Fees for damaged and lost materials include repair or replacement costs plus a $10.00 service charge.
The date due slip is a reminder of the day an item is due back in the library. As a service, the library sends out overdue notices, fine notices and statements. The library, however, levies fines even if the patron has not received notification. To view the status of materials checked out, refer to Circulation Policies which describes how to renew your books online (steps 1-6).
The library charges fines for overdue materials at the above rate until they are more than 21 days overdue. On the 22nd day, the library considers unreturned items lost. At that time, the library charges $10.00 plus the replacement cost (current retail or out-of-print price) for each lost item. The library then removes the fines that accumulated during the previous 21 days. Students are given sixty to ninety days to pay or dispute fines, service charges or material replacement fees. The library maintains these charges internally for a minimum of 60 days. Between the first and fifteenth of every month, the library transfers carried charges older than 60 days to student accounts.


Close your eyes and dream yourself away to a tropical island with the sound of the roaring ocean in the background. The Fruiticana series channels an exotic vibe and turns the kids' room into a paradise. The knitted fruits and fish double as both cushions and sweet, fluffy toys. Stuffed with the vibrant colours and bustling atmosphere of a market, the items hold hours of playtime with their rich embroidered surface with shimmering gold and silver detailing.


Welcome to Schemansky Sons Monuments. Our family owned and operated business has been proud to service the Detroit area for over a century. We understand that the passing of a loved one can be one of the most difficult times in your life. That's why we hold our compassionate, family oriented approach as central to our services. We believe in treating our customers right and helping them through a difficult period with compassion, respect and integrity.
We invite you to browse our site and learn more about what we do. In our Products and Services section, you can learn more about the various types of markers and monuments we offer. Over in the General Information area, you can learn more about the arts of headstone engraving and craftsmanship. If you would like to know more or have inquiries about any of our offerings, feel free to contact us online or by telephone at (313) 365-5390.


text:
Samsung Galaxy S9 and S9+ Pricing, Availability and Pre-order Out
Written by Joe Teh on February 26, 2018
This is a very long post. I copied and paste all those information that is needed for you to pre-order the Samsung Galaxy S9 or S9+ which commences from 1st March 2018. And on top of that, there is information on the pricing (including the 256GB variant).
Do spend some time to read through this if you really want to be the first to own the Samsung Galaxy S9 or S9+ when it launches here in Singapore.
Pre-Order and Registration of Interest
Pre-Order at Telecommunications Operators Pre-Order/ Registration of interest1 with telecommunication operators for the Galaxy S9 and S9+ will commence from 1 March 2018, Thursday, 12pm. Consumers can visit the following URLs for more information:
M1: www.m1.com.sg/galaxys9
Singtel: www.singtel.com/galaxys9
StarHub: www.starhub.com/galaxys9
Pre-Order at Samsung Store Online/ Samsung Experience Stores Consumers can also pre-order their Galaxy S9 and S9+ (without contract) via the Samsung Store online (http://www.samsung.com/sg/smartphones/galaxy-s9/shop/) from 1 March 2018, Thursday, 12pm or visit the following Samsung Experience Stores during opening hours:
Central: 313@somerset #B2-24/25/26 Tel: 6836 1809, Bugis Junction #01-54 Tel: 6338 7911, Chinatown Point #01-48 Tel: 6222 7911, Great World City #02-39 Tel: 6235 0985, Paragon #B1-27/27A Tel: 6735 5926, VivoCity #02-28/29 Tel: 6376 9150
East: Bedok Mall #B1-07 Tel: 6785 1118, Singapore Changi Airport Terminal 3 #02-23 Tel: 6241 4125 (Open to transit and departing passengers only), Parkway Parade #03-30F Tel: 6440 7969, Tampines Mall #02-29 Tel: 6782 9575
North: Causeway Point #03-12 Tel: 6891 1011, nex #04-42 Tel: 6636 7392
West: Jurong Point #B1-09/10/11 Tel: 6791 2272, Westgate #01-01 Tel: 6369 9175
Galaxy Studio, Central Court A, VivoCity, Level 1 (from 8 March 2018 onwards)
Pre-order at Major Consumer Electronics & IT Stores and Lazada Singapore
Pre-order for the Galaxy S9 and S9+ will also be available online from 1 March 2018, Thursday, 12pm at major consumer electronics & IT stores' (Best Denki, Courts, Gain City, Hachi, Harvey Norman and Newstead) respective websites and Lazada Singapore. More information is available at the following URLs:
Best Denki: https://www.bestdenki.com.sg/galaxys9
Courts: https://www.courts.com.sg/galaxys9
Gain City: https://www.gaincity.com/galaxys9
Hachi: https://www.hachi.tech/galaxys9
Harvey Norman: http://www.harveynorman.com.sg/galaxys9
Lazada Singapore: https://ali.lazada.sg/wow/i/sg/SGCampaign/galaxys9
Newstead: http://www.newstead.com.sg/galaxys9
All consumers who purchase Galaxy S9 or S9+ will be entitled to a complimentary Samsung Concierge Care Pack worth $128 and exclusive trade-in value for their eligible device of up to $610 2 via the Samsung Trade Up (SG) app, upon full payment during collection of their Galaxy S9 or S9+ from 10 March 2018. Purchasers of Galaxy S9+ (256GB3) will also receive a Wireless Charger Stand (Black) worth $108 4 during collection of their Galaxy S9+ (256GB3) upon full payment, on a while stocks last basis.
Local Pricing and Availability
The Galaxy S9 and S9+ will be available from 16 March 2018, at local telecommunication operators (M1, Singtel and StarHub), major consumer electronics & IT stores, Samsung Experience Stores and Lazada Singapore. The respective recommended retail prices for the devices are as follows:
Model, Built-in Memory3, RRP (S$)
Galaxy S9, 64GB, $1,198
Galaxy S9+, 64GB, $1,348
Galaxy S9+, 256GB, $1,498
The Galaxy S9 and S9+ will be available in Midnight Black, Coral Blue and Lilac Purple.
The following Galaxy S9 and S9+ accessories will also be available to complement the devices:
Accessory, Colour, RRP (S$)
Hyperknit Cover, Gray, Red, $48
Protective Standing Cover, Black, Silver, $68
Alcantara Cover, Black, Blue, Mint, Red, $68
Clear View Standing Cover, Black, Blue, Purple, Gold, $78
LED View Cover, Black, Blue, Purple, $88
DeX Pad, Black, $148
Wireless Charger Stand, Black, White, $108
Samsung Trade Up: Hassle-Free Trade Up from the Comfort of Home
Samsung today announced its new Samsung Trade Up Programme (provided by Brightstar Logistics Pte Ltd), that gives users a new hassle-free way to trade-in their old device. Consumers can enjoy convenience and great trade-in values, all through the Samsung Trade Up (SG) app, without the need to leave their homes. Exclusively available in conjunction with the launch of the new Galaxy S9 and S9+ in Singapore, consumers who purchased Galaxy S9 or S9+ can trade-in their old eligible devices5 via the Samsung Trade Up (SG) app to receive an exclusive trade-in value of up to $610 2.
With Samsung Trade Up Programme, it is now easier for consumers to own the Galaxy S9 and S9+.
With the Samsung Trade Up Programme, customers can have ample time to ensure that their important data and content from their old device are successfully transferred to their brand new Galaxy S9 or S9+, from the comfort of home.
Samsung Trade Up Programme
Consumers who purchased a Galaxy S9 or S9+ can do a Samsung Trade Up in 3 easy steps:
Download the Samsung Trade Up (SG) app on their old device5 (Available for download from 10 March 2018).
Do a quick assessment using the Samsung Trade Up (SG) app to valuate their old device.
Have the old device collected at their doorstep and receive the trade-in value via bank transfer.
READ Samsung announces GALAXY Mega in 2 sizes in Singapore
Consumers can visit www.samsung.com/sg/tradeup to learn more about Samsung Trade Up Programme.
Consumers who wish to purchase the Galaxy S9 or S9+ without a mobile contract may choose to head to the following Samsung Experience Stores from 10 March 2018 to 30 April 2018 to enjoy the Samsung Trade Up Programme in store. Consumers' old eligible device will be assessed on site and they will receive a discount amounting to the trade-in value from the purchase price of the Galaxy S9 or S9+6.
313@somerset (313 Orchard Road, #B2-24/25/26, Singapore 238895)
Bedok Mall (311 New Upper Changi Road, #B1-07, Singapore 467360)
Jurong Point (63 Jurong West Central 3, #B1-09/10, Singapore 648331) • VivoCity (1 Harbourfront Walk, #02-28/29, Singapore 098585)
Samsung Concierge Care Pack
The refreshed Samsung Concierge Care Pack, has been updated with more value-added services to provide consumers peace of mind by keeping their Samsung Galaxy device in tip-top condition. The new Samsung Concierge Care Pack has been refreshed based on the needs of consumers and their valuable feedback towards continuously improving the relevance of Samsung's services.
Samsung Concierge Care Pack (worth $128) is complimentary with every purchase of Samsung Galaxy S9 and S9+, and is valid for 12 months from the date of purchase of the new device7.
1-to-1 Device Exchange within 30 days Consumers can enjoy 1-to-1 exchange for functional defects within the first 30 days of their device purchase.
50% Savings for Out-of-warranty Repairs Consumers can enjoy a one-time 50% savings on out-of-warranty repair such as cracked screen, liquid damage, cosmetic repair, and more.
Service Support at Your Doorstep Consumers can receive a one-time personalised assistance an repair right at their doorstep
1-to-1 In-Box Accessories Exchange Consumers can enjoy 1-to-1 exchange for eligible in-box accessories with functional failure.
Diagnostic Device Checks Consumers can keep their Samsung Galaxy device in tip-top condition with diagnostic device checks performed by our friendly Samsung Customer Service Consultants.
Hassle-Free Data Transfer Consumers can receive dedicated switching service using Samsung Smart Switch from Samsung Customer Service Consultants.
Consumers who purchased the Galaxy Note8, Galaxy S8 and S8+ from 10 March 2018 onwards will also be able to purchase the Samsung Concierge Care Pack at a promotional price of $48 (usual
price $128) at Samsung Experience Stores or the following authorised Samsung Customer Service Centres:
Plaza Singapura (8 Orchard Road, #B2-23, Singapore 238839)
Westgate (3 Gateway Drive, #02-01, Singapore 608532)
VivoCity (1 Harbourfront Walk, #02-28/29, Singapore 098585)
Consumers can visit www.samsung.com/sg/samsungconcierge to learn more about Samsung Concierge.
Terms and conditions apply. Please check respective Telecommunication Operators' websites for details.
See www.samsung.com/sg/tradeup for the full list of eligible trade-in devices and their respective trade-in values from 1 March 2018. Trade-in value may vary, depending on the device condition. Samsung reserves the right to amend the list of eligible devices and their trade-in values at any time without prior notice.
Actual user-accessible internal memory is less than specified total memory due to storage of the operating system and software used to operate the device features, and other built-in applications, and may vary after software updates/ upgrades.
Complimentary gift is not exchangeable for cash or other items. Samsung reserves the right to substitute the gift as it deems necessary without prior notice. Please check stores for more details.
Available for download from Google PlayTM and Apple Store.
In-store discount is only available at the point of purchase of Galaxy S9 or S9+ at any of the stated Samsung Experience Stores. Any request for such discount after purchase of the Galaxy S9 or S9+ has been completed, will not be entertained in-store. Consumers who wish to trade-in their old device after purchasing the Galaxy S9 or S9+ will only be able to do so via the Samsung Trade Up (SG) app.
Terms & conditions apply, learn more at www.samsung.com/sg/samsungconcierge
Google Play is a trademark or registered trademark of Google LLC. Apple Store is a trademark of Apple Inc., registered in the U.S. and other countries.
Check out the local specs of the Galaxy S9 and S9+
Galaxy S9 and S9+ Product Specifications:
Built for the Way We Communicate Today: Samsung Galaxy S9 and S9+
The Samsung Galaxy S9 and S9+ fuel new discoveries with Super Slow-mo video, best-in-class low light camera and AR Emoji for a more personalized way to express yourself
BARCELONA, Spain – 25 February 2018 – Samsung Electronics Co., Ltd. introduces the Samsung Galaxy S9 and S9+, the smartphones that reimagine the way people communicate, share and experience the world. Made for an age in which consumers increasingly communicate and express themselves more with images, videos and emojis, the Galaxy S9 and S9+ drive innovation with Samsung's advanced camera. Redesigned with a new Dual Aperture lens that powers an innovative low light camera, Super Slow-mo video capabilities and personalized AR Emoji, the Galaxy S9 and S9+ ensure users do not miss a moment and make their every day epic.
READ Nokia Lumia 800 Colorful Accessories Revealed (Video)
The Galaxy S9 and S9+ deliver an enhanced entertainment experience with powerful stereo speakers tuned by AKG, immersive audio with Dolby Atmos® and a refined edge-to-edge Infinity Display1 – a key staple in Samsung's design heritage. In addition, the Galaxy S9 and S9+ will come with the new SmartThings app, which unites Samsung's existing IoT services into one single, smart experience.
"The way we use our smartphones has changed as communication and self-expression has evolved," said DJ Koh, president and Head of IT & Mobile Communications Division, Samsung Electronics. "With the Galaxy S9 and S9+, we have reimagined the smartphone camera. Not only do the Galaxy S9 and S9+ enable consumers to shoot great photos and videos anywhere, it's a smartphone that's designed to help them connect to others and express themselves in a way that's unique and personal to them."
Camera Reimagined
Today's cameras are for more than taking pictures – they're for connecting and communicating. Consumers want a smartphone camera with state-of-the-art technology, so they can express themselves with high-quality images and tools to tell their own, unique story. The Galaxy S9 and S9+ cameras are built with these consumers in mind, with a Super Speed Dual Pixel sensor with dedicated processing power and memory to take amazing shots with high photo quality. The Galaxy S9 and S9+'s camera features include:
Super Slow-mo: Make everyday moments epic with dynamic, slow-motion video that captures 960 frames per second. The Galaxy S9 and S9+ also offer automatic Motion Detection, an intelligent feature that detects movement in the frame and automatically begins to record – all users have to do is set up the shot. After capturing the Super Slow-mo video, users can select background music from 35 different options or add a tune from their favorite playlist. Users can
also easily create, edit and share GIF files with a simple tap in three playful styles of looping to watch the action over and over again.
Low Light Camera: Good lighting is the secret to any great photo. But often, photos are taken in less-than-ideal lighting conditions and most smartphone cameras have a fixed aperture that can't adjust to low or bright lighting environments resulting in grainy or washed out pictures. Similar to the way the iris of a human eye expands and contracts, Samsung's Dual Aperture2 (F1.5 / F2.4) automatically lets in more light when it's dark and less light when it's too bright, taking photos that are crisp and clear.
AR Emoji: Samsung lets users create an emoji that looks, sounds and acts like them. AR Emoji uses a data-based machine learning algorithm, which analyzes a 2D image of the user and maps out more than 100 facial features to create a 3D model that reflects and imitates expressions, like winks and nods, for true personalization. AR Emoji shares users' real-life emotions not only in video but also with a range of stickers and uses a standard AGIF file format so users can share their emojis across most third-party messaging platforms.
Bixby: Samsung's intelligence platform, integrated into the camera, uses augmented reality and deep learning technologies to provide helpful information about a user's surroundings3. With real-time object detection and recognition, Bixby instantly generates information directly on top of the image that the camera is pointing at. Users can translate foreign languages and currency in real time with Live Translation, learn about their surroundings, purchase products seen in the real world and track calories throughout the day4
Entertainment Reimagined
Smartphones are often our go-to choice for entertainment, which is why Samsung created a device that offers premium sound experiences with stereo speakers tuned by AKG. Whether users are watching their favorite movie or streaming their favorite artist's latest album, sounds are clear, crisp and rich in quality. The Galaxy S9 and S9+ also support Dolby Atmos, giving the effect of 360-degree sound.
The Galaxy S9 and S9+ audio experience is complemented by Samsung's revolutionary Infinity Display. First introduced on the Galaxy S8, the bold, bright Super AMOLED Infinity Display blends right into the phone with virtually no distracting notches. With adaptive contrast enhancement, users can use their device even in direct sunlight.
A Device that Fits with the Connected Lifestyle
As the first smartphone to support the new SmartThings app, the Galaxy S9 and S9+ are the central hub to manage every facet of the connected lifestyle at home, at the office or on the go. The SmartThings app will be introduced with the Galaxy S9 and S9+ and will connect to other Samsung and non-Samsung devices.
READ Introducing 5 New Nokia Phones with Return of Banana Phone, Nokia 8110
For those constantly on the move, the next-generation Samsung DeX empowers a mobile lifestyle by bringing a large, full-screen experience to the mobile handset. With the DeX Pad, a new docking system, users can easily connect the Galaxy S9 and S9+ to a larger monitor, keyboard and mouse to expand the mobile experience with enhanced document editing or even full-screen gaming5. Users can also transform the Galaxy S9 and S9+ into a Touch Pad with the DeX Pad6.
The Best Comes Standard with the Galaxy Foundation
Samsung sets the gold standard for smartphones with IP68 7 water and dust resistance and wireless charging and goes a step beyond with the Galaxy S9 and S9+. The devices now support expandable memory of up to 400GB with a Micro SD Card and are equipped with the latest premium application processors offering powerful performance and sophisticated image processing.
In addition, the Galaxy S9 and S9+ give users the peace of mind knowing that their phone is protected by Knox 3.1, Samsung's latest defense-grade security platform. The Galaxy S9 and S9+ support three different biometric authentication options – iris, fingerprint, and facial recognition – so users can choose the way they want to protect their device and applications. The devices feature Intelligent Scan, a new verification that intelligently uses the collective strength of iris scanning and facial recognition technology to quickly and conveniently unlock a user's phone in various situations. The Galaxy S9 and S9+ also introduce Dedicated Fingerprint, giving users the option to use a different fingerprint to access Secure Folder than the one used to unlock the phone.
The Galaxy S9 and S9+ take health to the next level with an improved optical sensor built directly into the device, providing richer, more accurate information on users' health status. This sensor allows the Galaxy S9 and S9+ to keep track of users' Heart Load Factor, a new measurement of the real-time demand placed on the heart8.
For more information about the Galaxy S9 and S9+, visit http://www.samsungmobilepress.com, news.samsung.com/galaxy or www.samsung.com.galaxy.
Samsung inspires the world and shapes the future with transformative ideas and technologies. The company is redefining the worlds of TVs, smartphones, wearable devices, tablets, digital appliances, network systems, and memory, system LSI and LED solutions. For the latest news, please visit the Samsung Newsroom at http://news.samsung.com.
*All functionality, features, specifications and other product information provided in this document including, but not limited to, the benefits, design, pricing, components, performance, availability, and capabilities of the product are subject to change without notice.
Infinity Display: a near bezel-less, full-frontal glass, edge-to-edge screen
The Dual Aperture supports F1.5 mode and F2.4 mode. Dual Aperture is installed on the rear camera (Galaxy S9) and rear wide-camera (Galaxy S9+).
Bixby service availability and features may vary by country or carrier. Voice Command recognizes English (U.S.), Mandarin Chinese and Korean. Not all accents, dialects and expressions are recognized. Voice command works with a select, growing list of Samsung and third-party apps. See "Apps with Voice" in Bixby for a list of compatible apps.
May differ by country and carrier.
Available on select Samsung smartphones running Android 8.0+. Using the original HDMI cable and charger included with DeX Pad is recommended. DeX Pad, keyboard, mouse, monitor sold separately.
DeX Pad comes with HDMI cable, wall charger and data cable. Accessories including monitor sold separately. Use of original HDMI cable and charger included with DeX Pad is recommended. Dex Pad also supports Galaxy S8, S8+ and Note8.
Based on test conditions for submersion in up to 1.5 meters of freshwater for up to 30 minutes. Rinse residue/dry if wet.
Intended for general wellness and fitness purposes only.
Screen measured diagonally as a full rectangle without accounting for the rounded corners.
Default resolution is Full HD+ and can be changed to Quad HD+ (WQHD+) in Settings.
May differ by country and carrier. User memory is less than the total memory due to storage of the operating system and software used to operate the device features. Actual user memory will vary depending on the operator and may change after software upgrades are performed.
Galileo and BeiDou coverage may be limited.
Android AR AR Emoji Augmented Reality Availability Emoji Featured Galaxy KNOX Pre-Order preorder Price Pricing ROI Samsung Samsung Galaxy Samsung Galaxy S9 Security Singapore Slow Motion Smart Phone SmartPhone
Canon Introduces New 4K Mirrorless EOS M50
Huawei P20 Official Launch Date and Venue is Out (Video)

redpajama_set_name: RedPajamaCommonCrawl


text:
The Spirit of Science Fiction, by Roberto Bolaño
Two young poets, Jan and Remo, find themselves adrift in Mexico City. Obsessed with poetry, and, above all, with science fiction, they are eager to forge a life in the literary world - or sacrifice themselves to it.
Roberto Bolaño's The Spirit of Science Fiction is a story of youth hungry for revolution, notoriety, and sexual adventure, as they work to construct a reality out of the fragments of their dreams.
But as close as these friends are, the city tugs them in opposite directions. Jan withdraws from the world, shutting himself in their shared rooftop apartment where he feverishly composes fan letters to the stars of science fiction and dreams of cosmonauts and Nazis.
Meanwhile, Remo runs headfirst into the future, spending his days and nights with a circle of wild young writers, seeking pleasure in the city's labyrinthine streets, rundown cafés, and murky bathhouses.
This kaleidoscopic work of strange and tender beauty is a fitting introduction for readers uninitiated into the thrills of Roberto Bolaño's fiction, and an indispensable addition to an ecstatic and transgressive body of work.


text:
Books by Daniel Klein
Released: Oct. 30, 2018
I THINK, THEREFORE I DRAW: UNDERSTANDING PHILOSOPHY THROUGH CARTOONS
by Thomas Cathcart, Daniel Klein
"Entertaining and slyly illuminating."
From Zeno to Nietzsche, a lighthearted, illustrated romp through philosophical thought. Read full book review >
EVERY TIME I FIND THE MEANING OF LIFE, THEY CHANGE IT: WISDOM OF THE GREAT PHILOSOPHERS ON HOW TO LIVE
by Daniel Klein
"A glossary explains the relatively few philosophical terms Klein sprinkles in this warm, winsome book of eclectic musings."
A miscellany of concise advice about life. Read full book review >
Reviewed: Jan. 29, 2013
NOTHING SERIOUS
"Klein has a light—or 'lite'—touch when it comes to both philosophy and love."
A hip editor takes the helm of Cogito, a stodgy philosophical journal, with mixed—and occasionally hilarious—results. Read full book review >
Released: Nov. 1, 2012
TRAVELS WITH EPICURUS: A JOURNEY TO A GREEK ISLAND IN SEARCH OF A FULFILLED LIFE
"Charming and accessible, this philosophical survey simply and accessibly makes academic philosophy relevant to ordinary human emotion."
A late-in-life reflection and modern-day philosophical exploration of what it means to age authentically. Read full book review >
THE HISTORY OF NOW
"Absorbing, nevertheless, though the novel never lives up to the promise of its vivid early chapters and enormously appealing characters."
How the past influences what follows, and how self-understanding inspires broader comprehension of all things: These are the themes of this gently philosophical family chronicle, the first volume of a planned trilogy. Read full book review >
VIVA LAS VENGEANCE
"Jarringly unfunny, and not much of a mystery either."
Fresh off a fling with costar Ann-Margret, an agitated Elvis Presley (Blue Suede Clues, 2002, etc.) decides to take a break in Vegas, out of whining range of the increasingly petulant Priscilla, his teenaged paramour. After taking in the act of insult comic Howie Pickles, who works over a big, blithe blond at the front table, Elvis falls a little in love with a voluptuous dancer named Shiva Ree. The dark-eyed beauty performs, along with a black panther, to hypnotic music unlike anything the King has ever heard. Shiva lives at the Center of the Light, an enclave dedicated to the study and practice of Eastern religion and customs. Before long, she's introduced Elvis to tantric sex and other less carnal disciplines. Meanwhile, a whodunit simmers in the background. The aforementioned blond, Bonnie Donaldsen, is found murdered shortly after attending Howie's show with Bruce, her new husband. In short order, there's a second victim, an Atlanta cop named J.P. Whaley, who had his own ringside seat at Howie's comedy show before his death, and, like Bonnie, his own connections to the Little (wedding) Chapel and a local bordello called the Bambi Ranch. An abrasive writer named Digby Ferguson, who wants to unravel the case, tries with limited success to get lovestruck Elvis involved. Under Shiva's influence, Elvis is planning an unusual "peace concert," at which the plot threads converge and most of the loose ends are tied up—not a moment too soon. Read full book review >
Released: March 18, 2002
BLUE SUEDE CLUES
"Klein's serviceable writing doesn't fulfill the promise of his idea. Surrounded by desperately unfunny cartoon suspects, his Elvis is a surprisingly generic sleuth, with few quirks and little appeal. Readers are likely to leave the building way ahead of him."
The King just can't get any respect in Hollywood. Colonel Parker's wearing him out with demeaning publicity stunts, and Ann-Margret's making trouble by announcing to the press that she and Mr. Presley are in love. What will his new bride Priscilla think? Trapped in fluffy vehicles like Kissin' Cousins, Elvis longs for a challenging role to display his acting chops. When he puts out a call for high-quality scripts, wackos come out of the woodwork with everything but. Even so, one appeal strikes his fancy. Stuntman Freddy Littlejon, a.k.a. Squirm, writes from prison to claim that he's been framed for the murder of starlet Holly McDougall. He encloses a picture of himself meeting Elvis, both in military uniforms. Elvis doesn't remember Squirm, but because he feels a special affinity for both stuntmen and servicemen, he turns sleuth for the second time (Kill Me Tender, 2000). The search takes him from a rodeo to the mean streets of Durango to the UCLA science lab, with stops at many Hollywood locations. Meantime, Squirm's suspiciously easy escape from prison makes the investigation a race against the clock. Multiple sets of twins, including both attorneys in Squirm's murder trial, run illogically through the story, triggering wistful flashbacks for Elvis, whose twin brother Jesse died at birth, and exasperation for everybody else. Read full book review >
Released: July 1, 2000
KILL ME TENDER
"More clichés than a hound dog has fleas. Klein, coauthor of Where's Elvis? (1998), hits every wrong note, from bad dialogue to unfunny farce. Skip the book; play the records."
Poor Elvis. First he was an unflattering postage stamp, now an unconvincing sleuth. With nothing much to do at Graceland except fend off the sycophants and down high-calorie breakfasts, the King decides to pay a condolence call when a young fan club member surprisingly succumbs to cardiac arrest. He's soon singing gospel on her church steps and being untrue to his intended, Miss Priscilla, with Miss Selma, a real fine black lady. Then two more fans die, a high-school gal pal now writing a tell-all book about Elvis follows, and all these deaths start to look suspicious. Could an Elvis impersonator be responsible—or a member of the King's inner circle? And who's taunting Elvis on those 45s delivered to Graceland? Elvis skips a recording session to investigate, consults a New York lesbian psychiatrist about possible motives (yeah, right), then learns about an instantaneously acting exotic poison from Miss Selma's boss, a medic treating po' black folk. He also runs afoul of a southern sheriff and manfully locks horns with many more cholesterol nightmares before he confronts the demented murderer in a scene as unlikely as his being named a spokesperson for the Vatican, or for Slim-Fast. Read full book review >


1. There's a web cam watching the park. From the Bulls web site click gameday, then stadium camera. Or you can click this.
2. After the tarp is taken back off the field, it's about 30 minutes before play begins.
If you're already at the game when the tarp is pulled out on the field, then, of course, you're out of luck. If it's a rainy day and you haven't left home yet, then just keep checking the webcam. If the tarp isn't on the field, then they are getting ready to play.
In my case it takes me about 30 minutes to get to the park. So once I see the tarp being rolled up I head out. That usually works. But sometimes the rain comes back.
You should know that the IL and their umpires really, really, really don't like to call a rain delay once a game has started. To actually postpone a game? Well, they are even more reluctant to do that. See that photo up top? They had not yet called the game.
That was, by the way, an amazing sight to see. Even Wool E. Bull got involved.


text:
Paraproctis is een geslacht van vlinders van de familie spinneruilen (Erebidae), uit de onderfamilie Lymantriinae.

Soorten
P. calamolopha Collenette, 1936
P. coulsoni Collenette, 1954
P. chionopeza Collenette, 1954
P. osiris Bethune-Baker, 1911

Donsvlinders

redpajama_set_name: RedPajamaWikipedia


text:
\section{Introduction}

The existence of multiple conformers for n-butane and higher n-alkanes has been known since the pioneering work of Pitzer.\cite{Pitzer1940} (See the introductions to Refs.\cite{Smi96,Allinger97,Deleuze02} for a detailed bibliography.) The importance of alkanes in particular --- as basic building blocks of organic chemistry and as constituents of fossil fuels --- requires no further elaboration, nor indeed does that of aliphatic chains in general --- as moieties of lipids, of polymers like polyethylene, or of nanosystems.

Modern high-accuracy theoretical thermochemistry methods, such as W4 theory developed at Weizmann\cite{W4,W4.4} and HEAT developed by a multinational consortium of researchers\cite{heat1,heat2,heat3} are capable of calculating bottom-of-the-well total atomization energies (TAE$_e$ values) with 95\% confidence intervals of 1 kJ/mol (0.24 kcal/mol) or less. For alkanes and other systems devoid of low-lying excited electronic states, the chief factors limiting accuracy of calculated total atomization energies (TAE$_0$) or heats of formation ($\Delta H^\circ_{f,0}$) at absolute zero are actually not of an electronic structure nature so much as the zero-point vibrational energies (ZPVEs), particularly the anharmonic corrections in them. At finite temperatures, this is compounded by the necessity of reliable heat content functions or enthalpy functions ($H_{298}-H_0$). By way of illustration, a component breakdown of heat content functions for a number of lower alkanes is presented in Table \ref{tab:TRC}.  For n-octane, the conformer contribution is seen to reach 1.05 kcal/mol. Clearly, when working in the kJ/mol accuracy region, one neglects such
contributions at one's peril.

Smith and Jaffe\cite{Smi96} studied conformational energies
of n-butane and the central torsion of n-hexane in considerable detail. For n-butane, they
obtained a trans-gauche energy of 0.59 kcal/mol at the CCSD(T)/cc-pVTZ//MP2/6-311G(2df,p) level. After correction, this was within 0.05 kcal/mol of the
then-latest experimental value by Herrebout et al.\cite{Durig}

Allinger et al.\cite{Allinger97} carried out a `focal point'\cite{focalpoint1,focalpoint2} convergence
study on the butane conformer energies and torsional barriers. Their best
estimate for the trans-gauche energy was 0.62 kcal/mol, just 0.04 kcal/mol lower than the very recent measurement by Balabin,\cite{Balabin2} 0.660 $\pm$ 0.022 kcal/mol.

A similar `focal point' study for n-pentane
was published by Salam and Deleuze\cite{Deleuze02} in 2002. Their best estimates
for the relative energies of the TG (trans--gauche), GG (gauche$^+$--gauche$^+$), and GX$^-$ (gauche$^+$--perpendicular$^-$) conformers are
0.621, 1.065, and 2.917 kcal/mol, respectively. Very recently, the TG and GG conformer energies were measured by Balabin\cite{Balabin2} as
0.618$\pm$0.006 and 0.940$\pm$0.020 kcal/mol, respectively. Note that the GG conformer is about 0.3 kcal/mol more stable than what one would expect from naively adding two TG energies: the GG conformer benefits from a mild dispersive stabilization (see, e.g., \cite{Osawa91,Balabin2}).

Tasi et al.,\cite{Tasi1} in their paper on the enumeration of conformers in
n-alkanes, discuss n-pentane at some length. Figure 1 in their paper is an
energy landscape of n-pentane in terms of the two CCCC torsion angles.
(In the remainder of this paper, we will adopt their notation for conformers:
g$^\pm$ for gauche torsion angles around $\pm$60$\deg$, x$\pm$ for `cross' or
`perpendicular' angles around $\pm$90$\deg$, and t for trans.)
It is seen there (as well as in the lower part of Figure \ref{fig:figure1} in the present paper) that the landscape has eleven minima: the global tt minimum,
two equivalent gg minima (g$^+$g$^+$ and g$^-$g$^-$), four equivalent tg minima (t$^+$g$^+$,
t$^+$g$^-$, g$^+$t, and g$^-$t), and finally four equivalent gx$^-$ minima (g$^+$x$^-$, g$^-$x$^+$,
x$^+$g$^-$, and g$^-$g$^+$). The gx- conformer is often, confusingly, labeled g$^+$g$^-$ in older literature:
in fact, the actual g$^+$g$^-$ structure is a transition state for a shallow barrier
between equivalent g$^+$x$^-$ and x$^+$g$^-$ structures (and similarly for g$^-$g$^+$ between
x$^-$g$^+$ and g$^-$x$^+$).

Because of this latter phenomenon (first pointed out, to the best of our knowledge, by
Osawa and coworkers,\cite{Osawa91}) higher $n$-alkanes have more conformers than
would be expected by naive "$3^n$" enumeration based on trans/gauche$^+$/gauche$^-$
products. This latter approach does lead to the correct four conformers for
$n$-pentane (even as it mislabels the energetically highest one), but only
yields ten unique conformers on the n-hexane surface while in reality
there are twelve. A graphical representation of the conformer space of n-hexane
can be seen in the upper part of Figure \ref{fig:figure1}.

While the ttt, gtt, tgt, tgg, gtg, gtg$^-$, and ggg conformers also occur
in the naive $3^n$ enumeration and the naive gg$^-$g conformer could be regarded
as a `rounded-off' equivalent of the actual xg$^-$x conformer, the naive ggg$^-$ and
gg$^-$t conformers actually each correspond to nonequivalent pairs, gx$^-$t/xg$^-$t
and gx$^-$g/ggx$^-$, respectively.

Tasi et al.\cite{Tasi1,Tasi2} defined rules for a more correct conformer
enumeration, based on pruning a $5^n$ search down by excluding `forbidden'
sequences that exhibit excessive sterical hindrance. The rules can be
summarized as follows:
\begin{itemize}
\item g$^+$g$^-$, g$^-$g$^+$,  x$^+$x$^-$, and x$^-$x$^+$ are forbidden. Instead, g$^+$x$^-$/x$^+$g$^-$ and g$^-$x$^+$/x$^-$g$^+$ pairs occur.
\item gx$^-$g, xgx$^-$, and their isomorphs are forbidden
\item xg$^-$g$^-$x and its isomorph x$^-$ggx$^-$ are forbidden
\end{itemize}

Under these rules, 30 and 95 nonequivalent conformers occur for n-heptane and
n-octane, respectively.

In the present work, we will first obtain benchmark ab initio conformer energies for $n$-butane, $n$-pentane, and $n$-hexane, using large basis set CCSD(T) as a `primary standard'. We will then show that double-hybrid functionals\cite{B2-PLYP,B2GP-PLYP} supplemented by an empirical dispersion correction yields results of essentially the same quality, and will proceed to use these as a `secondary standard'. Next, we will consider the performance of a variety of density functional methods for the conformers of the pentanes, hexanes, and selected heptanes and octanes. Finally, we will address the quality of computed thermodynamic corrections both by the more rigorous and the more approximate methods.

\section{Computational methods}

\subsection{Electronic structure}

All calculations were carried out using MOLPRO 2008.1\cite{molpro} or a locally modified version of Gaussian 03 rev. E.01\cite{g03} running on the Martin group Linux cluster at Weizmann. Gaussian was used for all DFT calculations as well as for MP2 optimizations: MOLPRO was used for the CCSD(T) calculations. Some post-CCSD(T) calculations were carried out using MRCC.\cite{MRCC}

The following DFT functionals were considered (grouped by rungs on the `Jacob's Ladder' of Perdew:\cite{JacobsLadder})
\begin{itemize}
\item second-rung (i.e., GGAs): BLYP,\cite{B88ex,LYPc} PBE\cite{PBE}
\item third-rung (i.e., meta-GGAs): M06L\cite{M06-L}
\item imperfect fourth rung (i.e., hybrid GGAs): B3LYP,\cite{B3,B3LYP} B3PW91,\cite{B3,PW91c} PBE0\cite{PBE0}
\item full fourth rung (i.e., hybrid meta-GGAs): B1B95,\cite{B88ex,B95c} PW6B95,\cite{PW6B95} BMK,\cite{BMK} M06,\cite{M06} M06-2X\cite{M06}
\item fifth rung: the double hybrids B2-PLYP,\cite{B2-PLYP} B2GP-PLYP\cite{B2GP-PLYP} and B2K-PLYP\cite{B2K-PLYP}
\end{itemize}

Most wavefunction ab initio calculations were carried out using the cc-pVnZ\cite{Dun89} and aug-cc-pVnZ\cite{Ken92} basis sets of Dunning and coworkers. In the course of this paper, we will refer to the cc-pVnZ basis set by the PVnZ acronym, and to the combination of aug-cc-pVnZ on carbon with regular cc-pVnZ on hydrogen by the AVnZ acronym (n=D,T,Q).

Most DFT calculations were carried out using the Jensen pc-2 basis set.\cite{pc-2}

Dispersion corrections for the DFT energies (denoted by the suffix "-D") were applied using our implementation of Grimme's expression:\cite{Grimme1,Grimme2}
\begin{equation}
E_{disp} = -s_{6} \sum_{i=1}^{N_{at}-1} \sum_{j=i+1}^{N_{at}} \frac{C_{6}^{ij}}{R_{ij}^{6}}f_{\rm dmp} \left(R_{ij} \right)\label{eq:grimme}
\end{equation}
where the damping function is taken as
\begin{equation}
 f_{\rm dmp} \left( R_{ij} \right) = \left[ 1 + \exp \left( -\alpha ( \frac{R_{ij}}{s_RR_{r}} -1 )\right)\right]^{-1}\label{eq:damping}
\end{equation}
and $C_{6}^{ij}\approx\sqrt{C_{6}^{i}C_{6}^{j}}$, $R_{r}=R_{{\rm vdW},i}+R_{{\rm vdW},j}$  is the sum of the van der Waals radii of the two atoms in question, and the specific numerical values for the atomic Lennard-Jones constants $C_{6}^{i}$ and the van der Waals radii (in this case, 1.452 \AA\ for C and 1.001 \AA\ for H) have been taken from Ref.\cite{Grimme1}. The length scaling $s_R$=1.0 and hysteresis exponent $\alpha$=20.0 were set as in Ref.\cite{Grimme2}.

This expression is left with a single functional-dependent empirical parameter, namely the prefactor $s_6$. This was taken from Refs.\cite{Grimme1,Grimme2} for BLYP, B3LYP, and PBE, from Ref.\cite{B2GP-PLYP} for the double hybrids, and from Ref.\cite{alkanes} for the remaining functionals. These were, for the most part, optimized against the S22 benchmark set of weakly interacting systems.\cite{Hobza06}

No corrections for intramolecular BSSE were made: instead, we elected to use basis sets sufficiently large ($spdf$ or $spdfg$ quality) that this should not be an issue on the accuracy scale of interest to us presently. We note that Balabin\cite{Balabin1} studied intramolecular BSSE for trans/gauche butane and selected hexanes in considerable detail.

\subsection{Other aspects}

The initial conformer structures were generated by stepping the CCCC dihedral
angles in 30 degree increments, running molecular mechanics optimizations on
all structures generated, and collating equivalent structures. In this manner,
both the unique conformer structures and their degeneracies are obtained in
an automated fashion.

The statistical thermodynamic corrections were then obtained by state summation
according to the method of Pitzer and Brewer.\cite{PitBrew} That is, the
partition function and its first two moments are obtained as follows:
\begin{eqnarray}
Q &=& \sum_i{d_i\exp\left(-\frac{E_i-E_0}{RT}\right)}\\
Q' &=& \sum_i{d_i\left(\frac{E_i-E_0}{RT}\right)\exp\left(-\frac{E_i-E_0}{RT}\right)}\\
Q'' &=& \sum_i{d_i\left(\frac{E_i-E_0}{RT}\right)^2\exp\left(-\frac{E_i-E_0}{RT}\right)}
\end{eqnarray}
where $E_i$ and $E_0$ are the energies of state $i$ and the ground state,
respectively (in molar units), R is the gas constant (replace by the Boltzmann
constant $k$ if molecular units are preferred for the energies), $d_i$ is the
degeneracy of the state, and T is the temperature in Kelvin.
The various thermodynamic functions are then obtained as:
\begin{eqnarray}
{\rm gef}(T)\equiv -\frac{G_T-H_0}{T}&=& R \ln Q\\
{\rm hcf}(T)=H_T-H_0&=& RT Q'/Q\\
S(T)=R\left(\frac{Q'}{Q}+\ln Q\right)\\
C_p(T)=R\left(\frac{Q''}{Q}-\left(\frac{Q'}{Q}\right)^2\right)
\end{eqnarray}

A slight complication is introduced when the internal partition function is
not assumed to be factorizable, i.e., each of the conformers is allowed to
have distinct rotational, vibrational, and (ignored in this work) electronic
partition functions. Then the following product rules apply (Eqs. 1-3 in
Ref.\cite{nh2}):
\begin{eqnarray}
Q=Q_0+\sum_i{\exp(-x_i)Q_i}\\
Q'=Q'_0+\exp(-x_i)\left[x_iQ_i+Q'_i \right]\\
Q''=Q''_0+\exp(-x_i)\left[x_i^2Q_i+Q''_i + 2 x_iQ'_i\right]
\end{eqnarray}
where the shorthand $x_i\equiv(E_i-E_0)/RT$ was applied.

While the expression for $C_p(T)$ is too clumsy for practical use, the
following equations express ${\rm gef}(T)$ and ${\rm hcf}(T)\equiv H_T-H_0$ in terms of the
quantities for the individual conformers:
\begin{eqnarray}
{\rm gef}(T)={\rm gef}(T)_0 + R \ln\left[1+\sum_i{d_i\exp(-x_i)\frac{Q_i}{Q_0}}\right]\\
{\rm hcf}(T)=\frac{{\rm hcf}_0(T)+\sum_i{\exp(-x_i)\frac{Q_i}{Q_0}[RTx_i+{\rm hcf}_i(T)] } }{1+\sum_i{\exp(-x_i)\frac{Q_i}{Q_0}}}
\end{eqnarray}

\section{Results and discussion}

\subsection{Wavefunction ab initio}

The wavefunction ab initio results are gathered in Table \ref{tab:ab-initio}. (Results in this section apply to MP2/cc-pVTZ reference geometries.)

\subsubsection{n-butane and n-pentane}

Applying W1 extrapolation\cite{W1} to CCSD(T)/PV\{D,T\}Z and CCSD/PV\{T,Q\}Z energies results in 0.598 kcal/mol. This is basically identical to our best result, 0.596 kcal/mol, which is obtained by W2 extrapolation\cite{W1} to CCSD(T)/PV\{T,Q\}Z and CCSD/PV\{Q,5\}Z data.
At the CCSD(T)/A'VQZ level, the trans-gauche conformer separation is 0.609 kcal/mol. The CCSD(T)/PVQZ result is insignificantly different (0.606 kcal/mol), as is the CCSD(T)/A'VTZ result (0.613 kcal/mol). CCSD(T)/PVTZ still comes quite close, at 0.588 kcal/mol (less than 0.01 kcal/mol below our best number): smaller basis sets exhibit more significant deviations (0.721 kcal/mol for A'VDZ, 0.693 kcal/mol for PVDZ).
Our best value is in excellent agreement with the experimental value of 0.67$\pm$0.10 kcal/mol of Herrebout et al.\cite{Durig} as well as the best calculation of 0.62 kcal/mol by Allinger et al.\cite{Allinger97}, and the 0.628 kcal/mol obtained by Klauda et al.\cite{Klauda} at what they term the MP2:CC level. (This is their shorthand for a procedure that is essentially MP2/PVQZ + [CCSD(T)/PVDZ -- MP2/PVDZ] at MP2/PVDZ reference geometries.)

Let us now considering the n-particle convergence with the cc-pVTZ basis set. SCF, as expected, overestimates the separation at 1.138 kcal/mol, while MP2 slightly overcorrects at 0.561 kcal/mol. However, the accidental very good agreement with the CCSD(T) number of 0.588 kcal/mol results from a fortunate error compensation: the gap widens to 0.664 kcal/mol at the MP3 level, to 0.635 kcal/mol at the MP4(SDQ) level, and to 0.653 kcal/mol at the CCSD level.

We considered the effect of post-CCSD(T) correlation by carrying out CCSDT(Q)/cc-pVDZ(no $p$ on H) calculations for both the trans and the gauche structures.
Connected quadruple excitations (Q) and higher-order triple excitation effects (i.e., the CCSDT -- CCSD(T) difference) are found to stabilize the gauche conformer by just 0.002 kcal/mol each: we conclude that post-CCSD(T) effects are insignificant on the accuracy scale we are interested in.

In the case of n-pentane, our best (W1h-val-type) estimates for the conformer energies of \{TG,GG,and GX$^-$\} relative to TT are
\{0.614,0.961,2.813\} kcal/mol, only marginally different from numbers are obtained from (T) contributions with the AVTZ basis set and CCSD contributions with the PVQZ basis set, \{0.605,0.954,2.810\} kcal/mol.
As expected, the CCSD(T)/AVTZ numbers are close at
\{0.586,0.946,2.817\} kcal/mol, as are the CCSD(T)/PVTZ numbers at \{0.581,0.919,2.767\} kcal/mol, even though the latter hint at an undershooting problem that will become clearer for n-hexane.
 The same general trends as for n-butane apply to n-particle convergence: MP2 slightly overcorrects, CCSD spaces conformers too wide. The MP2 error is largest for the GG conformer; the (T) contributions for the GG and GX$^-$ conformer energies are noticeably larger than for TG. The TG and GG values are in excellent agreement with the latest measurements by Balabin,\cite{Balabin2}
0.618$\pm$0.006 and 0.940$\pm$0.020 kcal/mol, respectively.

SCS-MP2\cite{SCS-MP2} yields conformer relative energies that are basically indistinguishable from CCSD.

Klauda et al.\cite{Klauda} report MP2:CC numbers of \{0.622,0.985,2.846\} kcal/mol, which are quite close to our higher-level data.
Our own MP2:CC calculation at our higher-level (MP2/cc-pVTZ) geometries yields slightly different numbers.

Our best estimates are somewhat different from those of Salam and Deleuze: \{0.621,1.065,2.917\} kcal/mol. Detailed analysis suggests that these differences are primarily due to their use of B3LYP/6-311++G(d,p) reference geometries. We shall see below that the B3LYP functional is inadequate for this purpose, not just in relative energies which are \{0.855,1.604,3.360\} at the B3LYP/6-311++G(d,p) level but also in terms of the calculated geometries: as can be seen in Table \ref{tab:dihedral}, the backbone torsion angles for the GG and GX$^-$ conformers are off by 5--6 degrees.

SCS-MP2 tracks the CCSD numbers quite closely, while SCS-CCSD clearly overcorrects for the (T) contribution.

The TT--GG energy difference appears to be the most sensitive to the level of theory, followed by the TT--GX$^-$ difference.

\subsubsection{n-hexane}

n-hexane, with its twelve conformers, becomes a bit unwieldy to compare in terms of individual conformer energies. One could instead focus on the calculated conformer contribution to the enthalpy function, which is the quantity that interests us most from an utilitarian point of view. However, by construction, this will be most affected by the low-lying gtt and tgt conformers.

Let us first consider the relative energies of the conformers at the W1h-val level. Obviously, the ttt conformer is lowest in energy, followed by nearly isoenergetic gtt and tgt conformers. Somewhat higher up is tgg, which is markedly more stable than gtg. gtg$^-$ is about 0.13 kcal/mol less stable than its cousin gtg, while ggg finds itself sandwiched between them. The remaining five conformers all have at least one `pentane interference' interaction: gxt and tgx- are nearly isoenergetic (and about 1.4 kcal/mol less stable than ggg), as is the less stable xg$^-$g$^-$ and gxg$^-$ pair, while the least stable conformer is xg$^-$x. Visual inspection reveals (see Electronic Supporting Information) that this latter conformer is basically a `helix', one end nearly coiling back over the other.

Klauda et al.\cite{Klauda} calculated MP2:CC relative energies for selected conformers: tgt 0.600, tgg 0.930, tgg$^-$ 2.740, gtg 1.180, gtg$^-$ 1.320 kcal/mol. We computed a complete set (Table II) at our own reference geometries, and find MP2:CC to agree with our W1h-val data to within about 0.01 kcal/mol. In contrast, CCSD(T)/cc-pVTZ data are biased downward by as much as 0.1 kcal/mol, presumably due to basis set superposition error.

\subsection{Density functional methods}

In order to basically eliminate the basis set as a factor in our comparison, we have used the extended pc-2 basis set throughout. Except for the double-hybrid results, a full optimization was carried out for every functional.

Let us begin by considering the pentane and hexane conformers. The energetic data are collected in Table \ref{tab:dft-ener}.

A few interesting features emerge. First, the percentage of Hartree-Fock exchange does not seem to be all that important: the BLYP/B3LYP pair on the one hand, and the PBE/PBE0 pair on the other hand, yield basically the same answers.

Second, while conventional DFT functionals (such as B3LYP, PBE0, B3PW91,...) tend to overestimate conformer gaps (progressively moreso as one goes higher up the conformer ladder), the M06 family of Truhlar underestimates them. Of particular note is the situation in pentane, where M06 wrongly finds the TG and GG conformers to be energetically nearly degenerate. Similarly distorted energetic pictures are seen for hexane conformers: we note, from considering the Grimme dispersion corrections for the various structures, that the GG interaction is favored by dispersion, and it appears that the M06 family overestimates that impact. The PW6B95 and BMK functionals, on the other hand, surprisingly do a much better  job.

Third, it was previously noted\cite{Chirality} that Grimme-type empirical dispersion corrections considerably improved DFT relative energies for selected conformers of 4-ethyl-4-methyloctane.
Comparing with a larger sample of higher-level reference data, however, we find that Grimme-type corrections appear to overcorrect for the conventional DFT functionals. Ad hoc reoptimization of $s_6$ prefactors revealed that, for alkane conformer energies, one would like a prefactor about 0.4-0.5 smaller than the generic optimum. For the M06 family, {\em ad hoc} optimized $s_6$ values are actually negative, which can be seen as ``undoing'' an overcorrection for dispersion.

Detailed inspection of dispersion correction contributions for the simplest case (the trans-gauche equilibrium in butane) reveals that dispersion interactions between the terminal CH$_3$ group and the CH$_2$ group in $\beta$ position relative to it ("1,3" interactions, if one likes) actually favor the trans conformer (as it has two $\beta$ hydrogens in close proximity rather than one), but that the gauche conformer enjoys much more favorable "1,4" dispersion interactions. The 1,3-interactions are in the distance range where the damping function, Eq.(\ref{eq:damping}), rapidly turns over, making the overall correction quite sensitive to its details. In addition some double-counting with the DFT correlation functional is inevitable.

Fourth, the double-hybrids B2GP-PLYP and B2K-PLYP perform fairly well even without dispersion corrections, and very well when supplemented with their standard dispersion corrections ($s_6$=0.40 for B2GP-PLYP-D and 0.30 for B2K-PLYP-D). Ad hoc optimization results in $s_6$ values that, unlike for the conventional functionals, are only slightly smaller than the standard values: $s_6$=0.28 for B2GP-PLYP and $s_6$=0.22 for B2K-PLYP. (Note that, if CCSD(T)/cc-pVTZ reference data were used instead for calibration, higher $s_6$ values of 0.32 for B2GP-PLYP and 0.26 for B2K-PLYP would result, which would lead to a downward bias for all conformer energies.) These results once again underline the robustness and versatility of the B2GP-PLYP and B2K-PLYP functionals. After {\em ad hoc} adjustment of $s_6$, the various double hybrids yield results of comparable quantity: in the remainder of the paper, we have somewhat arbitrarily restricted ourselves to B2K-PLYP as it requires the smallest adjustment to $s_6$, but we could have used B2GP-PLYP to equally good effect.

Fifth, the deficiencies of several functionals are not just reflected in the energetics, but also in the geometries. This is especially noticeable in the backbone torsion angles: Table \ref{tab:dihedral} contains the dihedral angles for the TG, GG, and GX$^-$ conformers of n-pentane by way of illustration.

As MP2/cc-pVTZ optimizations for all heptane and especially octane conformers would be computationally too unwieldy, we selected the PW6B95 functional for optimizing the reference geometries of the remaining conformers. Some exploratory calculations on pentane and hexane revealed that the 6-311G** basis set was adequately converged for our purposes, and that B2K-PLYP/pc-2 energetics at these reference geometries are very close to those obtained at MP2/cc-pVTZ geometries. The PW6B95/6-311G** level of theory was thus selected for the remaining conformer sets.

\subsection{n-heptane, n-octane, and the branched alkanes}

B2K-PLYP-D/pc-2//PW6B96/6-311G** relative conformer energies for all species considered in this paper can be found in Table \ref{tab:b2k-plyp}. We shall briefly survey the conformer sets here.
As an additional ``sanity check'' on our procedure, we have calculated the n-heptane conformer energies at the MP2:CC level as well. These results are compared with the B2K-PLYP-D(0.22)/pc-2 data in Table S1 of the Supporting Information. The two sets of values are in very close agreement with each other with an RMSD of just 0.04 kcal/mol. Refitting $s_6$ to this larger sample of 30 conformers revealed no significant change: $s_6$=0.224 RMSD, $s_6$=0.214 when fitted to RMSRelD, between which values $s_6$=0.22 is a good compromise. While n-heptane still has a pronounced ``band gap'' of sorts between the conformers involving only t and g interactions and the conformers involving x$^\pm$g$^\mp$ or g$^\pm$x$^\mp$ sequences, this gap becomes much smaller for n-octane.

Isopentane has just two conformers: the no-symmetry ground state conformer (with a "trans" backbone skeleton) and, around 0.79 kcal/mol higher, a gauche-like conformer with $C_s$ symmetry.

Isohexane (2-methylpentane) has seven conformers: these are best understood by substituting a methyl group on the four unique conformers of n-pentane. The ground-state conformer is TT; the TG and GT conformers become nonequivalent because of the methyl group; GX$^-$ and X$^-$G likewise become nonequivalent; and unlike for n-pentane, the GG conformer is actually the highest in energy here.

Isoheptane has some eighteen conformers, which are again best understood by substituting a methyl group on the 12 unique conformers of n-hexane and considering the resulting loss of  spatial degeneracy. Further details can be found in the Electronic Supporting Information.

Iso-octane, the "100\%" fixpoint on the octane scale, does not have the usual "2-methyl" backbone structure of the lower isoalkanes, but is effectively (t-butyl,isopropyl)methane. It has just three conformers, all without symmetry: in the global minimum, the iPr and tBU groups are oriented anti with respect to each other (fairly close to $C_s$ symmetry), while a "gauche" type structure is just 0.5 kcal/mol above and a third, "syn" like conformer, is found 3.3 kcal/mol above the global minimum.

3-methylpentane has six conformers.  The global minimum has $C_s$ symmetry: the other ones are best understood by considering n-pentane with a substituent in 3~position, making the fourfold degenerate TG and GX$^-$ conformer split up into nonequivalent pairs.

Biisopropyl (2,3-dimethylbutane) has just two conformers: the trans conformer with $C_{2h}$ symmetry and, less than 0.1 kcal/mol higher, the gauche conformer with $C_2$ symmetry.

Neoheptane has just three: the global minimum with $C_s$ symmetry and two asymmetric conformers at 2.3 and 2.7 kcal/mol higher. Their impact on the thermodynamic functions is minimal.

\subsection{Thermodynamic function corrections}

As pointed out in the introduction, one of the main motivations for the present study was a thermochemical one, namely the need for reliable conformer corrections to the enthalpy function and Gibbs energy function of the alkanes. Such data for the various species considered in this paper, as well as in Ref.\cite{alkanes}, can be found in Table \ref{tab:ef-gef} for various levels of theory.

As can be seen there, for the few systems where extended basis set CCSD(T) data are available, B2K-PLYP-D/pc-2 yields nearly identical results.
We thus take this level as our yardstick for the thermodynamic function corrections for the remaining species.

The enthalpy function correction --- which is what is needed for obtaining heats of formation from atomization energies, or vice versa --- exhibits fairly mild sensitivity to the level of theory. Broadly speaking, the M06 family tends to significantly underestimate the corrections while popular functionals like B3LYP tend to overestimate it. The anomalous negative sign for M06 and M06-L in the case of diisopropyl results from the wrong conformer ordering being predicted.

Sensitivity of the Gibbs energy function is rather more pronounced and behavior of the different functionals rather less systematic.

We finally address the issue of cross-coupling with zero-point and thermal corrections. Table \ref{tab:thermal-corrections}  compares B2K-PLYP-D/pc-2 thermal conformer corrections obtained in three different manners: (a) using bottom-of-the-well conformer energy differences ($\Delta E_e$); (b) using conformer energy differences at 0 K ($\Delta E_0$); (c) in addition, including individual rovibrational partition functions for all conformers (i.e., not assuming the rovibrational and conformer partition functions to be factorizable).
For want of a computationally affordable alternative, the RRHO (rigid rotor-harmonic oscillator) approximation was applied to both ZPVE and thermal corrections. (the molecular constants required were obtained at the PW6B95/6-311G** level with "ultrafine" integration grids, i.e., pruned (99,590) for energy and gradient and (50,194) for harmonic frequencies. For more on the sensitivity of harmonic frequencies to DFT integration grids, see Ref.\cite{grids}.) The thermochemical consequences of the RRHO approximation on the relative conformer energies are hard to quantify. The effects of (b) and (c) on the enthalpy function are generally quite modest for the n-alkanes (relatively speaking), but more pronounced for some of the branched alkanes, notably 3-methylpentane, isoheptane and isooctane. These general tendencies are exacerbated for the Gibbs energy function.

For n-butane through n-heptane, we considered internal rotation corrections for each individual conformer by means of the Ayala-Schlegel approximation\cite{AyalaSchlegel} . These results are given in the bottom pane of Table \ref{tab:thermal-corrections}. As can be seen there, the effect on the enthalpy functions is minimal, and that on the Gibbs energy function quite modest as well, considering that 0.1 e.u. translates to less than 0.03 kcal/mol in the free energy. We thus feel justified in not considering it for the other conformers.

Finally, one wonders about whether a CH$_2$ group equivalent could be applied to longer alkane chains. Linear regression of the corrections for n-butane through n-octane in terms of the number of backbone torsion angles reveals especially good correlation coefficients at the bottom of the well ($R^2$=0.9998 for $H_{298}-H_0$, 0.9993 for ${\rm gef}(T)$).
If zero-point energy is taken into account, we see a mild deterioration of the fit for $H_{298}-H_0$ but a somewhat more pronounced one for ${\rm gef}(T)$, while the fits including full thermal averaging become a bit noisier than desirable but still adequate for estimation purposes.

\section{Conclusions}

Conformational energies of n-butane, n-pentane, and n-hexane have been calculated at the CCSD(T) level and at or near the basis set limit. Post-CCSD(T) contribution were considered and found to be unimportant. The data thus obtained were used to assess the performance of a variety of density functional methods. Double-hybrid  functionals like B2GP-PLYP and B2K-PLYP, especially with a small Grimme-type empirical dispersion correction, are capable of rendering conformational energies of CCSD(T) quality. These were then used as a `secondary standard' for a larger sample of alkanes, including isopentane and the branched hexanes as well as key isomers of heptane and octane. Popular DFT functionals like B3LYP, B3PW91, BLYP, PBE, and PBE0 tend to overestimate conformer energies without dispersion correction, while the M06 family severely underestimates GG interaction energies. Grimme-type dispersion corrections for these overcorrect and lead to qualitatively wrong conformer orderings. All of these functionals also exhibit deficiencies in the conformer geometries, particularly the backbone torsion angles.
The PW6B95 and, to a lesser extent, BMK functionals are relatively free of these deficiencies.

Performance of these methods is further investigated to derive conformer ensemble corrections to the enthalpy function, $H_{298}-H_0$, and the Gibbs energy function, ${\rm gef}(T)\equiv - [G(T)-H_0]/T$, of these alkanes. These are essential for accurate computed heats of formation of especially the larger species, as the corrections for these are several times the expected uncertainty in modern computational thermochemistry methods such as W4 theory. While $H_{298}-H_0$ is only moderately sensitive to the level of theory, ${\rm gef}(T)$ exhibits more pronounced sensitivity. Once again, double hybrids acquit themselves very well.

The effects of zero-point energy and of nonfactorizable rovibrational partition functions were considered, and found to be smaller than those arising from an inadequate level of theory for the conformer energies.

\section*{Acknowledgments}
Research at Weizmann was funded by the Israel Science Foundation (grant 709/05),
the Helen and Martin Kimmel Center for Molecular Design, and the Weizmann Alternative Energy Research Initiative (AERI).
JMLM is the incumbent of the Baroness Thatcher Professorial Chair of Chemistry and a member {\em ad personam} of the Lise Meitner-Minerva Center for Computational Quantum Chemistry.

\section*{Supporting Information}

Optimized geometries in Cartesian coordinates of all conformers discussed here, as well as visualization of same using Jmol, can be viewed at the URL
\url{http://theochem.weizmann.ac.il/web/papers/alkane-conformers/}. PW6B95/6-311G** harmonic frequencies,  zero-point vibrational energies, and vibrational enthalpy functions of all conformers can also be found there, as can Table S-1.

\clearpage

\squeezetable
\begin{table}
\caption{Component breakdown of the theoretical enthalpy functions $H_{298}-H_0$ (kcal/mol) of several lower alkanes and comparison between theoretical and experimental values.\label{tab:TRC}}
\begin{tabular}{l|ccc|cccccc}
\hline\hline
 &  &  &  & \multicolumn{3}{c}{H$_{298}-$H$_0$}\\
 & & & & This work & \multicolumn{2}{c}{Expt.}\\
 & vibrational$^d$ & conformer$^e$ & Internal rotation$^d$ & Total &  CCCBDB$^a$\\
\hline
ethane         & 0.41 & 0.00 & 0.05 & 2.83 & 2.84\\
propane        & 1.08 & 0.00 & 0.09 & 3.54 & 3.52\\
n-butane       & 1.86 & 0.26 & 0.13 & 4.62 &  4.61\\
n-pentane      & 2.68 & 0.47 & 0.19 & 5.7 &  5.78\\
n-hexane       & 3.51 & 0.68 & 0.24 & 6.79 &  6.86\\
n-heptane      & 4.35 & 0.89 & 0.28 & 7.87 &  7.94$^b$\\
n-octane       & 5.20 & 1.08 & 0.35 & 8.97 &  9.03$^b$\\
isobutane      & 1.81 & 0 & 0.11 & 4.29 &  4.29\\
isopentane     & 2.65 & 0.09 & 0.19 & 5.3 &  5.26\\
neopentane     & 2.41 & 0 & 0.06 & 4.84 &  5.54$^c$\\
isohexane      & 3.45 & 0.24 & 0.21 & 6.28 &  6.29\\
3-methylpentane& 3.50 & 0.26 & 0.24 & 6.37 &  6.23\\
diisopropyl    & 3.44 & 0.04 & 0.22 & 6.07 &  5.85\\
neohexane      & 3.41 & 0 & 0.2 & 5.98 &  6.01\\
isoheptane     & 4.34 & 0.46 & 0.29 & 7.44 &  7.39$^b$\\
neoheptane     & 4.28 & 0.15 & 0.21 & 7.01 &  6.98$^b$\\
hexamethylethane&4.92 & 0 & 0.22 & 7.52 &  7.53$^b$\\
isooctane      & 5.02 & 0.16 & 0.22 & 7.77 &  7.69$^b$\\
\hline\hline
\end{tabular}
\begin{flushleft}
At room temperature, $[H_{298}-H_0]_{\rm trans+rot}$=4RT=2.37 kcal/mol for all practical intents and purposes.

$^a$ NIST CCCBDB\cite{cccbdb} unless indicated otherwise. Most of these data taken from next reference.\\
$^b$ Scott, D. W.;``Chemical Thermodynamic Properties of Hydrocarbons and related substances'', U.S. Bureau of Mines Bulletin No. 666 (US Government Printing Office, Washington, DC, 1974). Available online at \url{http://digicoll.manoa.hawaii.edu/techreports/PDF/USBM-666.pdf}. Indirectly (via TRC database) the source for most of the CCCBDB data.\\
$^c$ As shown in Ref.\cite{alkanes}, this value is erroneous.\\
$^d$ Ref.\cite{alkanes}.\\
$^e$ Present work, the values here may differ by 0.01--03 kcal/mol from the values given in the Supporting Information of Ref.\cite{alkanes} due to the use of a slightly different $s_6$ value for the B2K-PLYP-D functional (see text).\\
\end{flushleft}
\end{table}

\clearpage

\squeezetable
\begin{table}
\caption{Relative energies (in kcal/mol) of $n$-butane, $n$-pentane, and $n$-hexane conformers at MP2/cc-pVTZ reference geometries.\label{tab:ab-initio}}
\begin{tabular}{l|l|ccccc|cc|ccccc|cc}
\hline\hline
&  & \multicolumn{5}{c}{cc-pVTZ} & \multicolumn{2}{c}{aug-cc-pVTZ} & \multicolumn{5}{c}{cc-pVQZ} &  & \\
&  & HF & MP2 & SCS-MP2 & CCSD & CCSD(T) & CCSD & CCSD(T) & HF & MP2 & SCS-MP2 & CCSD & CCSD(T) & W1h-val$^a$ & MP2:CC\\
\hline
 & &\multicolumn{14}{c}{$n$-butane} \\
\hline
T & C$_{2h}$ & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000\\
G & C$_2$    & 1.138 & 0.561 & 0.657 & 0.653 & 0.588 & 0.679 & 0.613 & 1.147 & 0.578 & 0.674 & 0.673 & 0.606 & 0.611$^b$ & 0.620\\
\hline
 & &\multicolumn{14}{c}{$n$-pentane} \\
\hline
TT & C$_{2v}$ & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & & 0.000 & 0.000\\
TG & C$_1$    & 1.191 & 0.548 & 0.654 & 0.658 & 0.581 & 0.664 & 0.586 & 1.201 & 0.569 & 0.675 & 0.684 & & 0.614 & 0.613\\
GG & C$_2$    & 2.388 & 0.778 & 1.072 & 1.096 & 0.919 & 1.127 & 0.946 & 2.407 & 0.804 & 1.104 & 1.136 & & 0.961 & 0.977\\
GX$^-$ & C$_1$   & 4.275 & 2.783 & 2.972 & 2.957 & 2.767 & 3.008 & 2.817 & 4.292 & 2.811 & 3.002 & 3.002 & & 2.813 & 2.833\\
\hline
 & &\multicolumn{14}{c}{$n$-hexane} \\
\hline
TTT & C$_{2h}$ & 0.000 & 0.000 & 0.000 & 0.000 & 0.000  & & & 0.000 & 0.000 & 0.000 & 0.000 &  & 0.000 & 0.000 \\
GTT & C$_1$    & 1.203 & 0.517 & 0.633 & 0.639 & 0.558  & & & 1.213 & 0.539 & 0.656 & 0.666 &  & 0.595 & 0.589 \\
TGT & C$_2$    & 1.249 & 0.517 & 0.642 & 0.649 & 0.561  & & & 1.262 & 0.543 & 0.669 & 0.682 &  & 0.604 & 0.595 \\
TGG & C$_1$    & 2.499 & 0.706 & 1.033 & 1.070 & 0.871  & & & 2.521 & 0.741 & 1.076 & 1.124 &  & 0.934 & 0.930 \\
GTG & C$_2$    & 2.408 & 1.011 & 1.243 & 1.262 & 1.101  & & & 2.428 & 1.057 & 1.292 & 1.320 &  & 1.178 & 1.165 \\
G+T+G- & C$_i$ & 2.481 & 1.179 & 1.399 & 1.398 & 1.240  & & & 2.501 & 1.218 & 1.439 & 1.447 &  & 1.302 & 1.305 \\
GGG & C$_2$    & 3.696 & 0.914 & 1.429 & 1.487 & 1.180  & & & 3.727 & 0.951 & 1.482 & 1.553 &  & 1.250 & 1.260 \\
G+X-T+ & C$_1$ & 4.282 & 2.554 & 2.805 & 2.802 & 2.584  & & & 4.301 & 2.580 & 2.835 & 2.848 &  & 2.632 & 2.646 \\
T+G+X- & C$_1$ & 4.343 & 2.654 & 2.885 & 2.878 & 2.660  & & & 4.363 & 2.699 & 2.934 & 2.942 &  & 2.740 & 2.733 \\
G+X-G- & C$_1$ & 5.492 & 3.143 & 3.498 & 3.504 & 3.209  & & & 5.518 & 3.185 & 3.545 & 3.571 &  & 3.283 & 3.293 \\
X+G-G- & C$_1$ & 5.666 & 2.912 & 3.357 & 3.354 & 3.013  & & & 5.702 & 2.952 & 3.405 & 3.424 &  & 3.083 & 3.105 \\
X+G-X+ & C$_2$ & 7.787 & 4.860 & 5.275 & 5.237 & 4.855  & & & 7.824 & 4.900 & 5.322 & 5.312 &  & 4.925 & 4.947 \\
\hline\hline
\end{tabular}
\begin{flushleft}
$^a$SCF and CCSD energies extrapolated from cc-pV\{T,Q\}Z basis set pair, and the (T) contribution extrapolated from the cc-pV\{D,T\}Z basis set pair.\\
$^b$Using the augmented basis sets results in 0.598 kcal/mol.\\
\end{flushleft}
\end{table}
\clearpage

\squeezetable
\begin{table}
\caption{Comparison between various DFT functionals (pc-2 basis set, without dispersion correction) and our best conformer energies (kcal/mol) for $n$-butane, $n$-pentane, and $n$-hexane.\label{tab:dft-ener}}
\resizebox{1.00\textwidth}{!}
\begin{tabular}{l|c|ccccccccccccccc}
\hline\hline
 & Ref.$^a$ & B1B95 & B3LYP & BLYP & M06L & M06 & M06-2X & PBE0 & PBE & PW6B95 & B2GP-PLYP & B2K-PLYP & B2-PLYP & BMK & B3PW91 & MP2$^b$\\
\hline
 & &\multicolumn{15}{c}{$n$-butane} \\
\hline
T & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000\\
G & 0.598 & 0.778 & 0.898 & 0.925 & 0.393 & 0.466 & 0.522 & 0.820 & 0.813 & 0.712 & 0.986 & 0.990 & 0.986 & 0.703 & 0.968 & 0.561\\
\hline
 & &\multicolumn{15}{c}{$n$-pentane} \\
\hline
TT & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000\\
TG & 0.614 & 0.771 & 0.912 & 0.938 & 0.439 & 0.526 & 0.578 & 0.826 & 0.813 & 0.712 & 0.749 & 0.724 & 0.790 & 0.595 & 0.922 & 0.548\\
GG & 0.961 & 1.239 & 1.665 & 1.737 & 0.339 & 0.449 & 0.581 & 1.444 & 1.433 & 1.079 & 1.383 & 1.294 & 1.537 & 1.048 & 1.665 & 0.778\\
GX$^-$& 2.813 & 3.131 & 3.459 & 3.417 & 2.433 & 2.467 & 2.585 & 3.345 & 3.220 & 2.947 & 3.226 & 3.174 & 3.312 & 2.868 & 3.565 & 2.783\\
\hline
 & &\multicolumn{15}{c}{$n$-hexane} \\
\hline
TTT    & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000 & 0.000\\
GTT    & 0.595 & 0.768 & 0.905 & 0.928 & 0.355 & 0.427 & 0.502 & 0.820 & 0.803 & 0.702 & 0.726 & 0.699 & 0.773 & 0.651 & 0.914 & 0.517\\
TGT    & 0.604 & 0.808 & 0.942 & 0.960 & 0.441 & 0.500 & 0.541 & 0.861 & 0.839 & 0.745 & 0.750 & 0.719 & 0.804 & 0.745 & 0.957 & 0.517\\
TGG    & 0.934 & 1.361 & 1.763 & 1.839 & 0.400 & 0.527 & 0.641 & 1.542 & 1.536 & 1.193 & 1.410 & 1.306 & 1.586 & 1.143 & 1.769 & 0.706\\
GTG    & 1.178 & 1.548 & 1.834 & 1.884 & 0.783 & 0.893 & 1.004 & 1.665 & 1.640 & 1.415 & 1.477 & 1.417 & 1.580 & 1.326 & 1.855 & 1.011\\
G+T+G- & 1.302 & 1.608 & 1.871 & 1.908 & 0.845 & 1.065 & 1.178 & 1.714 & 1.669 & 1.479 & 1.563 & 1.517 & 1.641 & 1.454 & 1.890 & 1.179\\
GGG    & 1.250 & 1.823 & 2.595 & 2.728 & 0.390 & 0.594 & 0.751 & 2.238 & 2.252 & 1.561 & 1.983 & 1.822 & 2.258 & 1.586 & 2.597 & 0.914\\
G+X-T+ & 2.632 & 3.019 & 3.421 & 3.390 & 2.241 & 2.303 & 2.339 & 3.260 & 3.148 & 2.820 & 3.066 & 3.001 & 3.177 & 2.919 & 3.502 & 2.554\\
T+G+X- & 2.740 & 3.122 & 3.449 & 3.419 & 2.325 & 2.359 & 2.468 & 3.318 & 3.181 & 2.922 & 3.130 & 3.068 & 3.233 & 2.907 & 3.549 & 2.654\\
G+X-G- & 3.283 & 3.737 & 4.313 & 4.317 & 2.647 & 2.815 & 2.953 & 4.051 & 3.915 & 3.498 & 3.818 & 3.730 & 3.966 & 3.458 & 4.371 & 3.143\\
X+G-G- & 3.083 & 3.713 & 4.376 & 4.422 & 2.216 & 2.432 & 2.631 & 4.072 & 3.947 & 3.386 & 3.725 & 3.613 & 3.915 & 3.270 & 4.497 & 2.912\\
X+G-X+ & 4.925 & 5.566 & 6.227 & 6.207 & 4.199 & 4.480 & 4.514 & 5.957 & 5.734 & 5.199 & 5.593 & 5.501 & 5.750 & 5.179 & 6.406 & 4.860\\
RMSD$^c$&& 0.44 & 0.90 & 0.93 & 0.57 & 0.41 & 0.31 & 0.69 & 0.61 & 0.22 & 0.47 & 0.38 & 0.61 & 0.20 & 0.97 & 0.16\\
\hline
 & &\multicolumn{15}{c}{With standard "-D" dispersion correction} \\
RMSD$^d$&& 0.86 & 0.90 & 1.13 & 0.91 & 0.84 & 0.31 & 0.52 & 0.69 & 0.64 & 0.21 & 0.13 & 0.34 & 0.92 & 0.09 & 0.15\\
$s_6$&& 0.75 & 1.05 & 1.20 & 0.20 & 0.25 & 0.00 & 0.70 & 0.75 & 0.50 & 0.40 & 0.30 & 0.55 & 0.65 & 1.10 & (-0.16)\\
\hline
 & &\multicolumn{15}{c}{With {\em ad hoc} dispersion correction} \\
 RMSD$^e$&& 0.04 & 0.03 & 0.06 & 0.06 & 0.06 & 0.04 & 0.03 & 0.05 & 0.04 & 0.02 & 0.02 & 0.05 & 0.06 & 0.05 & \\
$s_6$&& 0.25 & 0.52 & 0.54 & (-0.33) & (-0.24) & (-0.18) & 0.40 & 0.35 & 0.13 & 0.28 & 0.22 & 0.36 & 0.11 & 0.56 & \\
\hline\hline
\end{tabular}}
\begin{flushleft}
$^a$Best values from Table \ref{tab:ab-initio}: W1h-val throughout.\\
$^b$cc-pVTZ basis set.\\
$^c$Over the $n$-hexane conformers, without dispersion correction.\\
$^d$Over the $n$-hexane conformers, with dispersion correction using standard s$_6$ values for the functionals (see text) given in the subsequent row.\\
$^e$Over the $n$-hexane conformers, with dispersion correction using {\em ad hoc} optimized s$_6$ values given in the subsequent row. Negative $s_6$
values can be seen as "undoing" an overcorrection in the underlying level of theory.\\
\end{flushleft}
\end{table}
\clearpage

\squeezetable
\begin{table}
\caption{Backbone torsion angles (degree) of the $n$-pentane conformers obtained with different DFT functionals in conjunction with the pc-2 basis set.\label{tab:dihedral}}
\begin{tabular}{l|l|cccccccccccc}
\hline\hline
Conformer & $\tau$  & B1B95 & B3LYP & B3PW91 & BLYP & BMK & M06-2X & M06-L & M06 & PBE0 & PBE & PW6B95 & MP2$^a$ \\
\hline
TG  & $\tau_1$  & 177.1 & 177.3 & 177.3 & 177.4 & 177.0 & 175.3 & 177.2 & 175.2 & 177.2 & 177.3 & 176.9 & 176.2 \\
    & $\tau_2$  & 64.7 & 66.2 & 66.0 & 66.8 & 64.1 & 61.6 & 62.3 & 62.7 & 65.3 & 65.7 & 64.5 & 64.0 \\
GG  & $\tau_1$  & 56.5 & 63.6 & 63.1 & 64.9 & 58.5 & 56.6 & 58.0 & 58.5 & 61.7 & 62.8 & 56.5 & 58.3 \\
GX$^-$ & $\tau_1$  & -98.3 & -90.9 & -90.9 & -89.3 & -97.8 & -95.8 & -92.5 & -94.4 & -93.9 & -91.7 & -98.0 & -96.4 \\
    & $\tau_2$  & 59.3 & 65.0 & 65.0 & 67.1 & 59.1 & 58.6 & 59.2 & 61.8 & 62.3 & 64.1 & 59.3 & 59.9 \\
\hline\hline
\end{tabular}
\begin{flushleft}
$^a$cc-pVTZ basis set.\\
\end{flushleft}
\end{table}

\squeezetable
\begin{table}
\caption{Relative energies, point groups, and degeneracies of the $n$-octane, $n$-heptane, isohexane, 3-methylpentane, isooctane, isoheptane, neopentane, and isopentane conformers at the B2K-PLYP-D(0.22)/pc-2//PW6B95/6-311G(d,p) level of theory (in kcal/mol).\label{tab:b2k-plyp}}
\resizebox{1.00\textwidth}{!}
\begin{tabular}{clcc|clcc|clcc|clcc}
\hline\hline
Degen. & Conformer & Symmetry & Energy & Degen. & Conformer & Symmetry & Energy & Degen. & Conformer & Symmetry & Energy & Degen. & Conformer & Symmetry & Energy\\
\hline
\multicolumn{4}{c}{\bf n-octane} & \multicolumn{4}{c}{\bf n-octane} & \multicolumn{4}{c}{\bf n-heptane} & \multicolumn{4}{c}{\bf isoheptane}\\
 1& TTTTT     &C$_{2h}$& 0.000 & 4 & G-G-TG-X+ & C$_1$ & 3.572  & 1 & TTTT    &C$_{2v}$& 0.000  & 2 & TTG-  & C$_1$ & 0.000\\
 4& TTTTG-    & C$_1$  & 0.584 & 4 & G+TG+G+X- & C$_1$ & 3.416  & 4 & TTTG-   & C$_1$  & 0.581  & 2 & TG+T  & C$_1$ & 0.306\\
 2& TTG-TT    & C$_2$  & 0.545 & 4 & G-G-TX-G+ & C$_1$ & 3.538  & 4 & TTG-T   & C$_1$  & 0.570  & 1 & TTG+  & C$_s$ & 0.778\\
 4& TTTG-T    & C$_1$  & 0.556 & 4 & TTG-X+G+  & C$_1$ & 3.164  & 4 & TTG-G-  & C$_1$  & 0.916  & 2 & G+TT  & C$_1$ & 0.539\\
 4& TTG-G-T   & C$_1$  & 0.822 & 4 & TX+G-TG+  & C$_1$ & 3.274  & 2 & TG+G+T  & C$_2$  & 0.860  & 2 & G+G+T & C$_1$ & 0.600\\
 4& TTTG-G-   & C$_1$  & 0.890 & 4 & TG+G+G+X- & C$_1$ & 3.369  & 4 & TG+TG+  & C$_1$  & 1.140  & 2 & G+TG- & C$_1$ & 0.690\\
 4& TTG-TG-   & C$_1$  & 1.098 & 4 & TTG-X-G+  & C$_1$ & 3.262  & 2 & G+TTG+  & C$_2$  & 1.148  & 2 & G+TG+ & C$_1$ & 1.445\\
 2& TG+TG+T   & C$_2$  & 1.099 & 4 & TG+X-G-T  & C$_1$ & 3.136  & 2 & G+TTG-  & C$_s$  & 1.152  & 2 & TX+G- & C$_1$ & 2.047\\
 2& G+TTTG+   & C$_2$  & 1.159 & 4 & G+G+TX-G+ & C$_1$ & 3.594  & 4 & TG+TG-  & C$_1$  & 1.265  & 2 & TG+X- & C$_1$ & 2.426\\
 4& TG+TTG+   & C$_1$  & 1.118 & 4 & TX+G-G-G- & C$_1$ & 3.224  & 4 & TG+G+G+ & C$_1$  & 1.186  & 2 & TG+G+ & C$_1$ & 3.025\\
 2& G+TTTG-   & C$_i$  & 1.156 & 4 & TG+TG-X+  & C$_1$ & 3.424  & 4 & G+TG+G+ & C$_1$  & 1.447  & 2 & X+G-G-& C$_1$ & 2.480\\
 4& TTG-G-G-  & C$_1$  & 1.123 & 4 & G+G+X-TG- & C$_1$ & 3.431  & 2 & G+TG-G- & C$_1$  & 1.606  & 3 & TX+G+ & C$_1$ & 2.784\\
 2& TG+G+G+T  & C$_2$  & 1.071 & 4 & G+TG-G-X+ & C$_1$ & 3.567  & 4 & G+G+G+G+& C$_2$  & 1.519  & 2 & G+X-G-& C$_1$ & 2.567\\
 4& TG+TTG-   & C$_1$  & 1.117 & 4 & G+G+TG-X+ & C$_1$ & 3.724  & 4 & TTX-G+  & C$_1$  & 2.674  & 2 & G+G+C+& C$_1$ & 3.404\\
 4& TG+G+TG+  & C$_1$  & 1.343 & 4 & TG+G+X-G- & C$_1$ & 3.192  & 4 & TTG-X+  & C$_1$  & 2.740  & 2 & G+X+G-& C$_1$ & 2.627\\
 4& TG+TG+G+  & C$_1$  & 1.368 & 4 & G+TX-G+G+ & C$_1$ & 3.591  & 4 & TG+X-T  & C$_1$  & 2.608  & 2 & G+G+X-& C$_1$ & 2.779\\
 4& TTG-TG+   & C$_1$  & 1.229 & 4 & G+G+G+G+X-& C$_1$ & 3.702  & 4 & TG+G+X- & C$_1$  & 2.956  & 2 & G+X+G+& C$_1$ & 3.466\\
 4& G+TTG+G+  & C$_1$  & 1.430 & 4 & G+TG+X-G- & C$_1$ & 3.778  & 4 & TX+G-G- & C$_1$  & 2.917  & 2 & X+G-T-& C$_1$ & 4.577\\
 4& G-TTG+G+  & C$_1$  & 1.434 & 4 & TG+X+G-G- & C$_1$ & 3.279  & 4 & G+TX+G- & C$_1$  & 3.261  & \multicolumn{4}{c}{\bf neoheptane} \\
 2& TG+TG-T   & C$_i$  & 1.246 & 4 & G+TG+X+G- & C$_1$ & 3.795  & 8 & G+TG+X- & C$_1$  & 3.329  & 1 & T     & C$_s$ & 0.000\\
 2& G+TG+TG+  & C$_2$  & 1.685 & 4 & G+TX-X-G+ & C$_1$ & 3.821  & 4 & G+TX-G+ & C$_1$  & 3.332  & 2 & X-    & C$_1$ & 2.256\\
 2& G+G+TG+G+ & C$_2$  & 1.656 & 4 & TG+X-G-G- & C$_1$ & 3.793  & 8 & TG+X+G- & C$_1$  & 3.280  & 2 & G-    & C$_1$ & 2.708\\
 4& TG+G+G+G+ & C$_1$  & 1.413 & 4 & G-X-G+G+G+& C$_1$ & 3.736  & 4 & TG+X-G- & C$_1$  & 3.220  & \multicolumn{4}{c}{\bf isopentane}\\
 4& G-G-G-TG- & C$_1$  & 1.634 & 4 & G+TG-X+G+ & C$_1$ & 3.881  & 4 & G+G+G+X-& C$_1$  & 3.506  & 2 & G+   & C$_1$ & 0.000\\
 4& TG+G+TG-  & C$_1$  & 1.495 & 4 & G+G+G+X+G-& C$_1$ & 4.115  & 4 & G+G+X-G-& C$_1$  & 3.413  & 1 & G-   & C$_s$ & 0.786\\
 4& TG+TG-G-  & C$_1$  & 1.574 & 4 & G+G+X-G-G-& C$_1$ & 3.863  & 2 & TX+G-X+ & C$_1$  & 4.636  & \multicolumn{4}{c}{\bf isooctane}\\
 4& G+TG-TG-  & C$_1$  & 1.822 & 4 & TG+X-X-G+ & C$_1$ & 4.804  & 4 & G+X-X-G+& C$_2$  & 4.897  & 2 & X-    & C$_1$ & 0.000\\
 2& G+G+G+G+G+& C$_2$  & 1.752 & 2 & TX+G-X+T  & C$_2$ & 4.223  & 4 & G+X+G-X+& C$_1$  & 5.426  & 2 & G-    & C$_1$ & 0.483\\
 4& G+TG-G-G- & C$_1$  & 1.805 & 4 & TTX-G+X-  & C$_1$ & 4.560  & 4 & L+G-X-G+& C$_1$  & 6.051  & 2 & X+    & C$_1$ & 3.319\\
 2& G+G+TG-G- & C$_i$  & 1.908 & 2 & G+X-TX-G+ & C$_2$ & 5.212  & 2 & X+G-G-X+& C$_2$  & 6.288  &  &       &       & \\
 2& G+TG-TG+  & C$_2$  & 1.959 & 4 & G+G+X-X-G+& C$_1$ & 5.183  &  \multicolumn{4}{c}{\bf isohexane}&&    &       & \\
 4& TTTX-G+   & C$_1$  & 2.658 & 2 & X+G-TG-X+ & C$_2$ & 5.508  & 2 & TG-     & C$_1$  & 0.000 &  &       &       & \\
 4& TTG-X+T   & C$_1$  & 2.507 & 4 & G+TX+G-X+ & C$_1$ & 5.248  & 2 & G+T     & C$_1$  & 0.352 &  &       &       & \\
 4& TTX-G+T   & C$_1$  & 2.561 & 4 & X+G-TX+G- & C$_1$ & 5.469  & 1 & TG+     & C$_s$  & 0.803 &  &       &       & \\
 4& TTTG-X+   & C$_1$  & 2.713 & 4 & G+TX-G+X- & C$_1$ & 5.255  & 2 & X+G-    & C$_1$  & 2.220 &  &       &       & \\
 4& TTG-G-X+  & C$_1$  & 2.883 & 4 & X+G-TX-G+ & C$_1$ & 5.488  & 2 & G+X-    & C$_1$  & 2.533 &  &       &       & \\
 4& TX+G-TG-  & C$_1$  & 3.140 & 4 & TX+G-X+G+ & C$_1$ & 5.078  & 2 & G+G+    & C$_1$  & 3.165 &  &       &       & \\
 4& TX+G-G-T  & C$_1$  & 2.702 & 2 & G+X-TX+G- & C$_i$ & 5.544  & 2 & X+G+    & C$_1$  & 2.983 &  &       &       & \\
 4& TG+TG+X-  & C$_1$  & 3.303 & 4 & TX+X+G-X+ & C$_1$ & 5.328  & \multicolumn{4}{c}{\bf 3-methylpentane}&&&     & \\
 4& G+TTG+X-  & C$_1$  & 3.255 & 2 & X+G-G-G-X+& C$_2$ & 5.544  & 2 & TG      & C$_1$  & 0.353 &  &       &       & \\
 4& G+TTX-G+  & C$_1$  & 3.171 & 2 & X+G-TG+X- & C$_i$ & 5.700  & 2 & G-T     & C$_1$  & 0.115 &  &       &       & \\
 4& TTX-G+G+  & C$_1$  & 2.880 & 4 & X+G-G-X-G+& C$_1$ & 5.803  & 2 & G-G-    & C$_1$  & 0.630 &  &       &       & \\
 4& G+TTX+G-  & C$_1$  & 3.228 & 2 & G+X-X-X-G+& C$_2$ & 5.914  & 1 & G-G+    & C$_s$  & 0.000 &  &       &       & \\
 4& TG+X-TG-  & C$_1$  & 3.127 & 4 & TG+X-G-L+ & C$_1$ & 5.913  & 2 & T-T     & C$_1$  & 1.862 &  &       &       & \\
 4& G+TTG-X+  & C$_1$  & 3.254 & 4 & G+G+X+G-X+& C$_1$ & 6.128  & 2 & C+G-    & C$_1$  & 3.222 &  &       &       & \\
 4& TG+TX+G-  & C$_1$  & 3.213 & 2 & G+X+G-X+G+& C$_2$ & 5.942  &  &         &        &       &  &       &       & \\
 4& TG+X-TG+  & C$_1$  & 3.237 & 4 & X+G-X+X+G-& C$_1$ & 6.991  &  &         &        &       &  &       &       & \\
 4& TG+TX-G+  & C$_1$  & 3.287 & 4 & L+G-X-G+X-& C$_1$ & 8.083  &  &         &        &       &  &       &       & \\
\hline\hline
\end{tabular}}
\begin{flushleft}
\end{flushleft}
\end{table}
\clearpage

\squeezetable
\begin{table}
\caption{Enthalpy function (H$_{298}-$H$_0$) and Gibbs energy function calculated with various DFT functionals with the pc-2 basis set.\label{tab:ef-gef}}
\begin{tabular}{l|ccccccccccccc}
\hline\hline
& B1B95 & B2K-PLYP & B2K-PLYP-D & B3LYP & BLYP & M06-2X & M06 & M06-L & PBE & PBE0 & PW6B95 & CCSD(T) & W1h-val$^a$ \\
\hline
& \multicolumn{12}{c}{H$_{298}-$H$_0$  (kcal/mol)}\\
\hline
n-butane          & 0.272 & 0.269 & 0.256 & 0.274 & 0.273 & 0.237 & 0.222 & 0.199 & 0.274 & 0.274 & 0.267 & 0.254 & 0.252\\
n-pentane         & 0.513 & 0.497 & 0.468 & 0.514 & 0.514 & 0.435 & 0.395 & 0.336 & 0.514 & 0.513 & 0.504 & 0.462 & 0.473\\
isopentane        & 0.090 & 0.090 & 0.092 & 0.085 & 0.083 & 0.093 & 0.093 & 0.087 & 0.086      & 0.087      & 0.091  & \\
n-hexane          & 0.757 & 0.726 & 0.678 & 0.748 & 0.746 & 0.608 & 0.546 & 0.464 & 0.750 & 0.750 & 0.746 & 0.663 & 0.686\\
isohexane         & 0.267 & 0.269 & 0.243 &       &       & 0.164 & 0.170 &0.148  & 0.278      &  0.271     &  0.261 & \\
3-methylpentane   & 0.308 & 0.303 & 0.265 & 0.326 & 0.322 & 0.168 & 0.150 & 0.154 & 0.327 & 0.326 & 0.294 & \\
diisopropyl       & 0.009 & 0.055 & 0.041 &    0.025   & 0.018 & 0.037 &-0.075 & -0.164 & 0.055      & 0.056      & 0.003  & \\
n-heptane         & 1.005 & 0.960 & 0.886 & 0.942 & 0.921 & 0.840 & 0.837 & 0.649 & 0.966 & 0.974 & 0.991 & & 0.893$^b$\\
isoheptane        & 0.520 & 0.513 & 0.456 & 0.583 & 0.487 & 0.353 & 0.401 & 0.286 & 0.530      & 0.525      & 0.506  & \\
neoheptane        & 0.160 & 0.129 & 0.147 &       & 0.138 & 0.223 & 0.221 & 0.257 &       & 0.115      & 0.183  & \\
n-octane          & 1.250 & 1.190 & 1.076 & 1.178 & 1.153 & 0.946 & 0.942 & 1.250 & 1.209 & 1.250 & 1.222 & \\
isooctane         & 0.167 & 0.161 & 0.156 &0.169 &0.170 &0.147 &0.128 &0.134 &0.167 &0.167&0.164 & \\
\hline
& \multicolumn{12}{c}{Gibbs energy function (cal/K.mol)}\\
\hline
n-butane          & 0.856 & 0.910 & 1.053 & 0.724 & 0.696 & 1.199 & 1.286 & 1.407 & 0.815 & 0.808 & 0.935 & 1.073 & 1.088\\
n-pentane 		   & 1.704 & 1.758 & 2.090 & 1.367 & 1.317 & 2.379 & 2.570 & 2.805 & 1.576 & 1.550 & 1.864 & 2.135 & 2.080\\
isopentane 		   & 1.592 & 1.596 & 1.625 & 1.556 & 1.546 & 1.651 & 1.684 & 1.778 & 1.560      &  1.569     & 1.606  & \\
n-hexane 		   & 2.454 & 2.632 & 3.166 & 1.982 & 1.917 & 3.654 & 3.927 & 4.264 & 2.283 & 2.238 & 2.708 & 3.286 & 3.148\\
isohexane 		   & 2.265 & 2.215 & 2.466 &       &       & 2.851 & 2.849 & 2.997 & 2.047      &  2.066     & 2.378  & \\
3-methylpentane    & 2.808 & 2.797 & 3.004 & 2.543 & 2.506 & 3.408 & 3.471 & 3.458 & 2.579 & 2.614 & 2.897 & \\
diisopropyl  	   & 2.153 & 1.993 & 2.043 &   2.099    &  2.124     & 2.056 & 2.427 & 2.706 & 1.993      & 1.991      & 2.172  & \\
n-heptane 		   & 3.262 & 3.512 & 4.284 & 2.392 & 2.229 & 4.693 & 4.795 & 5.499 & 2.850 & 2.834 & 3.603 & & 4.256$^b$\\
isoheptane 	   	   & 3.093 & 3.118 & 3.574 & 2.452 & 2.343 & 4.008 & 3.957 & 4.410 & 2.693      & 2.724      & 3.292  & \\
neoheptane 		   & 0.145 & 0.105 & 0.125 &       & 0.113 & 0.232 & 0.225 & 0.288 &       & 0.091      & 0.176  & \\
n-octane 		   & 4.091 & 4.436 & 5.451 & 2.946 & 2.720 & 6.186 & 6.346 & 4.091 & 3.552 & 4.091 & 4.559 & \\
isooctane 		   & 1.994 & 2.055 & 2.111 &1.943& 1.910 &2.196 &2.313 &2.313&1.980&1.981&2.038 & \\
\hline\hline
\end{tabular}
\begin{flushleft}
B2K-PLYP and B2GP-PLYP results at PW6B95/6-311G(d,p) geometries. Geometries fully optimized at remaining levels of theory for butane, pentane, hexane, and neoheptane, but PW6B95/6-311G(d,p) reference geometries used for remaining heptanes and octanes.\\
CCSD(T) results at MP2/cc-pVTZ geometries, using AVQZ basis set for n-butane, AVTZ basis set for n-pentane, and PVTZ basis set for n-hexane.\\
$^a$SCF and CCSD energies extrapolated from cc-pV\{T,Q\}Z basis set pair, and the (T) contribution extrapolated from the cc-pV\{D,T\}Z basis set pair.
$^b$MP2:CC result.
\end{flushleft}
\end{table}
\clearpage

\squeezetable
\begin{table}
\caption{B2K-PLYP-D(0.22)/pc-2//PW6B95/6-311G(d,p) thermal conformer corrections at 298.15K using three approximations: (a) using  `bottom of the well' conformer energy differences; (b) using the same at 0 K; (c) accounting for individual rovibrational partition functions.\label{tab:thermal-corrections}}
\begin{tabular}{l|ccc|ccc}
\hline\hline
 & \multicolumn{3}{c}{gef(T) in e.u.} & \multicolumn{3}{c}{H$_{298}-$H$_0$ in kcal/mol}\\
 & just $\Delta E_e$ & just $\Delta E_0$ & vib.avg. & just $\Delta E_e$  & just $\Delta E_0$ & vib.avg.\\
\hline
$n$-butane & 1.053 & 1.067 & 1.149 & 0.256 & 0.255 & 0.267\\
$n$-pentane & 2.090 & 1.748 & 2.539 & 0.468 & 0.489 & 0.508\\
$n$-hexane & 3.166 & 2.651 & 3.419 & 0.678 & 0.718 & 0.682\\
$n$-heptane & 4.284 & 3.632 & 4.628 & 0.886 & 0.934 & 0.826\\
$n$-octane & 5.466& 4.528& 5.301& 1.081 & 1.193 &1.025\\
3-methylpentane & 3.004 & 2.632 & 2.429 & 0.265 & 0.324 & 0.229\\
diisopropyl & 2.043 & 2.088 & 1.981 & 0.041 & 0.028 & 0.031\\
isoheptane & 3.573 & 3.086 & 2.761 & 0.456 & 0.516 & 0.401\\
isohexane & 2.466 & 2.149 & 1.893 & 0.243 & 0.271 & 0.173\\
isooctane & 2.111 & 2.000 & 1.849 & 0.156 & 0.165 & 0.122\\
isopentane & 1.625 & 1.568 & 1.568 & 0.092 & 0.087 & 0.084\\
neoheptane & 0.125 & 0.075 & 0.027 & 0.147 & 0.100 & 0.033\\
\hline
\multicolumn{7}{c}{Linear regression for n-alkanes (\# of backbone torsions)}\\
\hline
slope & 1.102 & 0.881 & 1.039 & 0.207 & 0.232 & 0.183\\
intercept & -0.094 & 0.083 & 0.289 & 0.053 & 0.021 & 0.111\\
$R^2$ & 0.9993 & 0.9964 & 0.9882 & 0.9998 & 0.9993 & 0.9928\\
\hline
\multicolumn{7}{c}{With individual internal rotation corrections for each conformer}\\
\hline
$n$-butane  & 1.030 & 1.043 & 1.125 & 0.259 & 0.257 & 0.270\\
$n$-pentane & 2.138 & 1.778 & 2.557 & 0.466 & 0.493 & 0.508\\
$n$-hexane  & 3.246 & 2.704 & 3.458 & 0.672 & 0.723 & 0.682\\
$n$-heptane & 4.408 & 3.716 & 4.686 & 0.873 & 0.939 & 0.824\\
\hline\hline
\end{tabular}
\begin{flushleft}
\end{flushleft}
\end{table}

\begin{figure}
\includegraphics[width=15cm,angle=0]{figure1composite.pdf} \\
\caption{Graphical representation of the conformers of $n$-pentane (bottom) and $n$-hexane (top). The more
purple the marker, the lower the conformer is in energy. Degeneracies are noted in square parentheses.\label{fig:figure1}}
\end{figure}

\clearpage

redpajama_set_name: RedPajamaArXiv


text:
Das Kugelstoßen der Frauen bei den Leichtathletik-Halleneuropameisterschaften 2017 fand am 3. März 2017 in der Kombank-Arena in Belgrad statt. Im Finale setzte sich mit Weltjahresbestleistung von 19,24 Metern die Ungarin Anita Márton vor der Bulgarin Radoslawa Mawrodiewa und der Belarussin Julija Leanzjuk durch. Als beste Deutsche belegte Claudine Vita den fünften Platz mit der persönlichen Bestleistung von 18,09 Metern.

Rekorde

Im Finale verbesserte Anita Márton ihre eigene europäische Jahresbestleistung und die Weltjahresbestleistung im dritten Versuch auf 19,24 Meter und im sechsten Versuch auf 19,28 Meter.

Resultate

Qualifikation
Die Qualifikation fand am 3. März 2017 um 10:50 in der Kombank-Arena statt.

Finale
Das Finale fand am 3. März 2017 um 17:35 in der Kombank-Arena statt.

Weblinks
 Ergebnislisten: Qualifikation und Finale
 Results (englisch) auf der EAA-Webseite

Halleneuropameisterschaften 2017, Kugelstosen der Frauen


text:
› Switzerland – COVID-19: Closing Borders, Limiting Entry
Switzerland – COVID-19: Closing Borders, Limiting Entry and Visa Issuance FAQs
Switzerland – COVID-19: Closing Borders, Limiting Entry
As an additional step in the fight against COVID-19, Switzerland closed around 130 border crossing points on Tuesday, 17 March 2020, and is now channeling entry only via designated border crossing points. There are special restrictions with respect to five Schengen countries: Italy, France, Germany, Austria, and Spain. New rules in place essentially mean that Switzerland will no longer will issue Schengen visas for 90 days or until further notice. National visas (i.e., visas for stays of more than 90 days) for nationals subject to visa requirements are also only to be issued in exceptional cases.
Travel/Border Crossing Restrictions, and Limitations on Visa Services
Q&A – What Does It Mean for You?
Adrian Tüscher
Director, Attorney-at-Law, Head of Employment & Immigration Services
KPMG AG/SA
As an additional step in the fight against COVID-19, Switzerland closed around 130 border crossing points on Tuesday, 17 March 2020, and is now channeling entry only via designated border crossing points.1
Switzerland, like many other countries, is limiting cross-border travel into the country with significant impact for the mobility of a company's international workforce. The closing – for the most part – of Switzerland's borders and other travel, entry-exit, and visa handling matters that have been announced, will impact companies with assignee populations in terms of existing and future assignments inbound to Switzerland or outbound from Switzerland. Employees and their families who may have received offers for an international assignment to Switzerland may need to postpone the commencement of the assignment – or may indeed be already there but on limited term visas. This could cause some anxiety, stress, and inconvenience, especially where plans for relocation are already underway or where they are already in Switzerland on temporary visas.
The changes will require employers to re-consider their personnel and work arrangements due to travel limitations and work permit restrictions.
Travel Restrictions for Italy, France, Germany, Austria, and Spain
Only Swiss citizens and any persons who have to travel to Switzerland for professional reasons or who otherwise have to enter the country for exceptionally urgent and necessary reasons are permitted to enter by air or land if they are coming from a non-European Union (EU) country or from these five Schengen countries: Italy, France, Germany, Austria, and Spain. Even though Liechtenstein borders Switzerland, entry from the country is not yet restricted as Liechtenstein and Switzerland share the same customs region.
Transit and transportation of goods are still permitted.
No Entry Visas to Be Issued for Next Three Months
With a few exceptions, entry at the Schengen external borders is strictly prohibited.2 Switzerland is thus following the practice of the other Schengen countries. This essentially means that Switzerland will no longer issue Schengen visas for 90 days or until further notice.
National visas (i.e., visas for stays of more than 90 days) for nationals subject to visa requirements are also only to be issued in exceptional cases. Exceptions relate to family members of Swiss citizens who are subject to a visa and have been granted permission for a Swiss residence permit, as well as specialists from the health sector.
Can people still enter Switzerland for work purposes?
Yes. Although most companies have ordered employees to work from home, some companies may still require their employees to be present (health sector, production of goods, etc.). If you hold a valid work permit for Switzerland, you are still permitted to enter for work reasons. It is recommended that your employer issue a letter confirming the necessity of your travel to your work-place.
Are visits to family and friends in Switzerland allowed?
It depends. If you are entering from one of the above-mentioned five countries or from a non-EU country, your entry to Switzerland will most likely be denied for the time being.
If you require a Schengen visa to enter Switzerland, no Schengen visas will be issued for the next three months.
If the points above do not apply, entry may be permitted for now. However, restrictions can be extended at any time.
In general, any non-essential travel should be avoided as new travel restrictions can be enacted anytime and channeling of entry at certain border points can lead to big delays.
Can employees with a valid visa authorisation letter obtain an entry visa?
No. The Federal Council is suspending the issuance of Schengen visas and national visas for third-country nationals for an initial period of three months. Employees – even if their application may be approved by the Swiss authorities – will not receive the required visa for themselves and their family members. As a result, they may not take up work in Switzerland (initially) for the next three months. Visa authorisations are valid for three months. This deadline can be extended by another three months to avoid the authorisation becoming expired once the travel restrictions have been suspended.
Can family members of Swiss citizens obtain an entry visa?
Yes. People married to a Swiss citizen who have a residence permit in Switzerland are still allowed to enter. In case you need an entry visa, the responsible Swiss embassy will issue one.
Can Swiss citizens claim support for repatriation from the government?
It depends. Since 16 March 2020, the Federal Council has been recommending Swiss travellers abroad return to their place of residence as long as this is still possible. Otherwise they risk getting stuck abroad. By law, Swiss citizens cannot claim an organised repatriation from a crisis area or in a crisis situation. All travellers are responsible for their own return home.
The Federal Department of Foreign Affairs (FDFA) supports travel agencies and airlines when it comes to obtaining landing permits or extending deadlines. If required – as anticipated for some destinations – Switzerland will organise return trips.3 That is possible, but complex. In addition, the funds are limited.
KPMG NOTE
Companies should consider the wider implications for any foreign employees who may over-stay due to difficulties of returning home. There can be consequences around immigration, personal tax, and permanent establishment risk.
The KPMG Immigration Team in Switzerland will endeavour to update you regularly on the rapidly evolving situation when important developments occur.4
1 A list of border crossing points that are closed (PDF 52 KB).
3 For more information on Swiss travellers who are still abroad, see "Swiss travellers abroad should register on the 'Travel Admin App'".
4 For information on the Swiss federal government's steps to address the COVID-19 situation, see in French; in German; in Italian; in Romansch.
Additionally, for information on measures taken by the Swiss federal government to combat COVID-19, see the U.S. Embassy in Switzerland webpage.
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* Please note that KPMG LLP (U.S.) does not provide immigration services. However, KPMG Law LLP in Canada can assist clients with U.S. immigration matters.
The information contained in this newsletter was submitted by the KPMG International member firm in Switzerland.
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Flash Alert is an Global Mobility Services publication of KPMG LLPs Washington National Tax practice. The KPMG logo and name are trademarks of KPMG International. KPMG International is a Swiss cooperative that serves as a coordinating entity for a network of independent member firms. KPMG International provides no audit or other client services. Such services are provided solely by member firms in their respective geographic areas. KPMG International and its member firms are legally distinct and separate entities. They are not and nothing contained herein shall be construed to place these entities in the relationship of parents, subsidiaries, agents, partners, or joint venturers. No member firm has any authority (actual, apparent, implied or otherwise) to obligate or bind KPMG International or any member firm in any manner whatsoever. The information contained in herein is of a general nature and is not intended to address the circumstances of any particular individual or entity. Although we endeavor to provide accurate and timely information, there can be no guarantee that such information is accurate as of the date it is received or that it will continue to be accurate in the future. No one should act on such information without appropriate professional advice after a thorough examination of the particular situation.
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