The Norsat Wayfarer is an industrial strength transportable satellite communication system built strong for the most demanding users working with the most challenging applications and environments. The Wayfarer is fully automated, integrated, and versatile enough for deployment virtually anywhere, including mobile field offices, field vehicles, or directly on the ground. A complete satellite solution, the Wayfarer includes everything to meet your communication needs.
The Norsat Wayfarer includes a heavy duty motorized azimuth/elevation powder coated steel superstructure, glass fibre reinforced polyester antenna (SMC), motorized feed assembly, LNB, BUC, inclinometer, GPS, modem, Ethernet switch, and a system controller. Completely assembled, the stowed chassis fits into the bed of a standard pickup for quick and effortless deployment.
With the push of a single button the Norsat Wayfarer allows the user to easily point, acquire and peak on a satellite, without the use of additional specialized tools. The Wayfarer comes equipped with 'built in intelligence' that simplifies the acquisition process. With a fast acquire time and simple setup, the Wayfarer can be easily deployed without technical expertise.
The Norsat Wayfarer has been used extensively throughout many of the resource industries and has a proven track record of success though hard rains, strong winds, and other extreme environmental conditions.


In celebration of the Safer Internet Day, Google details in a blog post the different ways that users could protect their accounts from compromise. While the search giant noted that it is doing its best to protect people's security and privacy, the company also stated that people should still perform several basic steps on their own to strengthen their online security.
Users could prevent malicious individuals from taking control of the person's accounts by creating unique passwords for different accounts. In a survey conducted in December 2018, 65% of users reuse their password for multiple accounts, with 13% of respondents further saying that they apply the same password for all their accounts.
The search giant noted that using the same password will result in the compromise of multiple accounts once criminals successfully take over one account. Google admits that it could be difficult for users to create and remember multiple passwords, so the search giant recommends people to use password managers or even write down the passwords in a piece of paper stored in a safe place.
Moreover, just in case someone obtains the person's passwords, using two-factor authentication (2FA) will still prevent other people from controlling user's accounts. The 2FA adds an additional step into the login process that requires anyone logging in to enter codes provided by a text message or an application, respond to a prompt received on a trusted device, or connect a hardware security key. If the person fails to perform the required steps, they will still not gain access to the account even if they know its password.
In the unfortunate occasion of account compromise, setting up a recovery email or mobile device will help online services inform its subscribers of possible suspicious activity. It will also allow users to block people who use the account without permission as well as to regain control of their account.
Background: Google repeatedly highlights the importance of online security through posts on its official blog, and it also developed ways that would make it easier for consumers to protect their information online. For example, Google launched the Google Prompt back in 2017, an authentication method that uses trusted devices to verify people's identities with a single tap. Furthermore, Google also released the Titan Security Keys, which serves a physical defense against security breaches. Since switching to physical security keys, Google states that there has been no successful phishing attempt on its employees.
Impact: While Google and other tech firms continue to develop ways to ensure the security of its users, there are still steps that people must take to ensure that their accounts remain protected. Given that more services are now done online which include communication and banking, compromise of accounts can severely affect a person's life, so users should take their online security more effectively.


You must go to a castle near Edea's house and put both eyes in the statue at the top, get the code, then do the same to the one at the bottom and enter the code. Then go into the open door and beat Odin. If you don't beat him by the time the time runs down, its game over.
You must kill 20 Tonberrys to make the Tonberry King appear.
Lolipolooza Canyon - It's near Timber.
To summon Kochocobo, you must first find a chocobo forest. Then get the whistle and push square button and pick "HELP". Chocoboy will catch one for you. Whether or not you decide to ride one, you now have the ability to summon Kochocobo using Gystall greens that you buy from Chocoboy.
To beat Diablos easily, follow this method: Draw demis from him (DON'T CAST DEMI!). Use the demis you drew from him and he will throw a curaga at you. He does this every time you hit him with your own demi. Keep doing this until the demis only take away 100-900 off of him. Then start summoning GFs.
Take the Ragnorok to the southwest corner of the world map and land on the floating platform (secret research facility). While inside, don't move while the light is on. Go to the strange light and inspect it. Pick the first option and fight a ruby dragon. Then pick the 2nd option and fight another ruby dragon. Then pick the 3rd option (hidden) to fight Bahamut. After you beat him, leave the research facility and push the triangle button to go into the Ragnorok. Then talk to your party members. If you want Eden, land on the platform again. This time there should be a save point. Climb down the ladder onto the ground, then inspect the machine on the left and it will open the door. Use the following blocks in a row: 2,2,1,1,2. Then let Zell work the machine and go down into the dungeon. When you get down there, add the final blocks and you will fight the Ultima Weapon. Draw from him to obtain Eden. Warning:You must beat him to get Eden. He is very hard.
At the top of the staircase by the entrance.
At the top of the large staircase, swing on the swinging light, through the door.
In the room with paintings.
In the Tomb room (get the key at the fountain).
Across the chandelier (use 1 party to go to a party-changing point by the broken stairs, then the others to go across the chandelier into a room with a seal guard).
When you unlock some of your abilities, you should have a chance against Ultimecia.
Here's how to get to him: Take the party who you want to fight up to the fountain room and change parties. Next, use your other party to go up the stairs to the right and you should see a rope. Pull it, and you will be timed. Switch parties again. Now go into the organ room to find the Omega Weapon standing there. Pretty much everything heals him, so don't use elemental attacks or magic on him. Here's my strategy (its not the only way): Use a hero if you have any. Try to use limit breaks. Rinoa's Invincable moon is very important. Don't use Zell's My final heaven. Try to use Pheonix Pinion. It heals him, but if you die, he may revive you. Use a meltdown.


A Parenting Life: Happy ten year Anniversary to Mr Awesome and I!
And just between you and me I couldn't think of a more lovelier place to celebrate it than alongside the the Pentecost River with the Cockburn Ranges as the back drop. Sure there will be no recommitment ceremony or party as I originally thought we would for this momentous occasion but it turns out I am more than ok with that.
This is day two at Home Valley Station and I am just loving it. This is exactly what I signed up for.
In a bid to escape the crowds we elected to stay at the riverside campsite and in the generators allowed section. We are already working out that old Jenny is not necessarily appreciated by many so we figured that fewer people will be found where they are permitted.
This meant we pretty much had the entire section to ourselves while up to ten other groups crammed in together on the other side. Totally winning.
As much as we had decided to be as far away as possible from the main homestead today being such a special day and all we figured it would be a good excuse to hang by the pool and go to dinner at the restaurant. It also provided me with the opportunity to catch up with some much over due washing.
Being the tropical kind of people that we are though and the weather being a good five degrees or more cooler than what we are acclimatised to the swimming part didn't last too long. There was however a lovely playground that the children were happy to make good use of.
Dinner turned out to be a surprisingly expensive experience but this surprise may also have been on account of us not actually dining out all that often. Initially I was disappointed by the fact that kangaroo was not available that day. There was a rather deliciously sounding roo salad I was keen to try. My second choice was to have the barramundi, which normally I don't do when eating out. Having had many a fresh caught one cooked at home rarely is it done better. This however was one of the rare occasions and oh my goodness it was just about the best tasting fish I have ever had the pleasure to put between my lips.
The real highlight of the night was the drive home. Not only did we get to see some wild dingoes on the road but the two little ones fell asleep on the way meaning there was no bed time fights! Which meant Mr Awesome and I had plenty of time to stare at the Milky Way and look for shooting stars.


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We invite children to spend their time after school actively and have fun! We organise hobby groups and summer camps to teach children to get to know horses, make friends with them, take care of them, and ride correctly. During the training, we tell children about the horses kept in the stud farm, their story, breeds, sports and other achievements, horse anatomy and hygiene, teach them how to use equipment and control a horse, as well as organise educational games, sporting and art events.
Children and young people aged between 6 and 16 years are welcome to our hobby groups and camps.
Anyone wishing to improve their riding skills can join our hobby groups as well. Experienced trainers and winners of various competitions work with children involved in professional equestrian sports.


Someone has got to go. Either you or the mold.
And no one's ever heard of a person deferring their house and belongings to a mold colony.
You can take back your home and eliminate the mold growing inside of it. Even better?
You don't have to hire an expensive contractor. Here are 4 sure ways to help clean mold and help you to breathe easy again.
1. Use a wet vacuum.
Wet vacuums are used to remove water from the floor, carpets and hard surfaces. This is of crucial importance following a water incident like a flood or a ceiling leak. It's important to wet vacuum all of the water and dry as much of the area as possible.
Even after this step, there is still more drying to do. Make sure not to use a wet vacuum to vacuum any porous material without liquid; otherwise you could be spreading more spores. Vacuums should also be cleaned and dried after use, preventing mold spores from developing inside your secret weapon.
Mold can usually be removed from hard surfaces by wiping the spot down with water and detergent. It is important to clean the area thoroughly and equally important to dry the surface after a wipe down. Mold needs moisture to develop, and a spot that's left undried can start the whole process all over again.
3. Use a HEPA Vaccuum.
HEPA vacuums (High Efficiency Particulate Air) are recommended for the final step of clean up. After an area has been dried and any contaminated materials extracted, the HEPA filtered vacuum can clean up the the remaining dust that might have settled on the surface.
The HEPA filter is the industry standard in trapping unclean air particles from pollutants; wipe out the next generation of mold before it has a chance to start growing.
Sadly, there may come a time when mold growth has become too widespread in a furniture piece and it cannot be salvaged. This often times happens after a major water incident such as a flood or sewage line break. It is better to discard the item than risk exposing yourself to harmful mold, if it cannot be cleaned or is not worth the effort. However, even when disposing of an object be sure to keep the disposal sanitary.
Moldy items should be double bagged using 6-mil polyethylene sheeting. This prevents the mold spores from spreading to other areas of the house on the way out. It might also be a good idea to seal the bag shut with duct tape. Often times porous materials such as upholstered furniture has to be thrown away if it has been soaked in soiled water. In porous materials, molds grow on or fill in the empty crevices of the material, which makes it extremely difficult to clean completely.
These are the most effective methods in mold remediation. If you can think of a better way, then try it. One way or the other, get rid of the mold and restore your house to a healthy living environment.


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Kristen Cloke (* 2. September 1968 in Van Nuys, Kalifornien) ist eine US-amerikanische Schauspielerin.

Leben
Cloke gab ihr Schauspieldebüt 1990 in dem Film Megaville. Danach war sie bis in die 2000er Jahre hinein vor allem in Fernsehproduktionen zu sehen.

Bekannt wurde sie durch die Rolle der Shane Autumn Vansen in der Science-Fiction-Serie Space 2063 aus dem Jahre 1995. Kristen Cloke ist seit dem 13. Juni 1998 mit dem Produzenten Glen Morgan verheiratet und wurde am 21. Juni 2002 Mutter ihres Sohnes. Im Juni 2004 bekam das Paar sein zweites Kind, eine Tochter.

Filmografie (Auswahl)
 1990: Megaville
 1991: Die blonde Versuchung (The Marrying Man)
 1991: Exzesse im Frauenknast (Caged Fear)
 1992: Zurück in die Vergangenheit (Quantum Leap, Fernsehserie, Episode 5x07)
 1992: Höllische Spiele (Stay Tuned)
 1993: Diagnose: Mord (Diagnosis Murder, Fernsehserie, Episoden 1x06–1x07)
 1993: Cheers (Fernsehserie, Episode 11x12)
 1995–1996: Space 2063 (Space: Above and Beyond, Fernsehserie, 23 Episoden)
 1996: Akte X – Die unheimlichen Fälle des FBI (The X-Files, Fernsehserie, Episode 4x05)
 1997: The Rage – Im Rausch der Gewalt (The Rage)
 1997–1998: Millennium – Fürchte deinen Nächsten wie Dich selbst (Millennium, Fernsehserie, 10 Episoden)
 2000: Final Destination
 2003: Willard
 2006: Black Christmas
 2009: Men of a Certain Age (Fernsehserie, Episode 1x01)
 2011: Magnificat
 2011: Pretty Little Liars (Fernsehserie, Episode 1x14)
 2017: Lady Bird

Weblinks

 Offizielle Website (englisch)

Einzelnachweise

Filmschauspieler
US-Amerikaner
Geboren 1968
Frau

redpajama_set_name: RedPajamaWikipedia


Michael Hahn, Vice President at Samsung C&T America conducted a seminar for about 55 attendees at last week's MAGIC trade show in Las Vegas. Hahn discussed Samsung C&T's wholesale fashion business model which supports brands as they grow their business without giving up any equity.
With Samsung as a partner, BB Dakota has increased their business every year and in 2015 launched Cupcakes and Cashmere's first fashion collection.
Read more Samsung fashion industry success stories.


1. If you consider it a sport to gather your food by drilling through 18 inches of ice and sitting there all day hoping that the food will swim by, you might live in Michigan.
2. If you're proud that your region makes the national news 96 nights each year because Pellston is the coldest spot in the nation, you might live in Michigan .
3. If your local Dairy Queen is closed from November through April, you might live in Michigan.
4. If you instinctively walk like a penguin for five months out of the year, you might live in Michigan.
5. If someone in a store offers you assistance, and they don't work there, you might live in Michigan.
6. If your dad's suntan stops at a line curving around the middle of his forehead, you might live in Michigan.
7. If you have worn shorts and a coat at the same time, you might live in Michigan.
8. If your town has an equal number of bars and churches, you might live in Michigan.
9. If you have had a lengthy telephone conversation with someone who dialed a wrong number, you might live in Michigan .
10. "Vacation" means going up north on I-75.
11. You measure distance in hours.
12. You know several people who have hit a deer more than once.
13. You often switch from "heat" to "A/C" in the same day.
14. You can drive 65 mph through 2 feet of snow during a raging blizzard, without flinching.
15. You see people wearing camouflage at social events (including weddings).
16. You install security lights on your house and garage and leave both unlocked.
17. You carry jumper cables in your car and your girlfriend knows how to use them.
18. You design your kid's Halloween costume to fit over a snowsuit.
19. Driving is better in the winter because the potholes are filled with snow.
20. You know all 4 seasons: almost winter, winter, still winter and road construction.
21. You can identify a southern or eastern accent.
22. Your idea of creative landscaping is a statue of a deer next to your blue spruce.
23. You were unaware that there is a legal drinking age.
24. Down South to you means Ohio .
25. A brat is something you eat.
26. Your neighbor throws a party to celebrate his new pole barn.
27. You go out to a fish fry every Friday.
28. Your 4th of July picnic was moved indoors due to frost.
29. You have more miles on your snow blower than your car.
30. You find 0 degrees "a little chilly."
31. You drink pop and bake with soda.
32. Your doctor tells you to drink Vernors and you know it's not medicine.
33. You can actually drink Vernors without coughing.
34. You know what a Yooper is.
35. You think owning a Honda is Un-American.
36. You know that UP is a place, not a direction.
37. You know it's possible to live in a thumb.
38. You understand that when visiting Detroit , the best thing to wear is a Kevlar vest.
39. You actually understand these jokes, and you forward them to all your Internet friends!
Not bad. But an incomplete list. I would add a few more.
40. If twelve judges in your county share the same five last names between them, you might live in Michigan.
41. If everyone you know thinks there is a trench at the southern border of your county, never to be crossed by white people headed south, you might live in Michigan.
42. If you can stand on the southern border of your county and can count four burned out buildings on the other side of the line, you might live in Michigan.
43. If, one year later, you stand on the same spot, and still count the same four burned out buildings (with a serious likelihood you may count a couple more), you might live in Michigan.
44. If you can visit your own childhood neighborhood and find that 80% of the houses are still occupied by the same people who occupied them when you were in elementary school 40 years earlier, you might live in Michigan.
45. If you can only visit your childhood city parks if you live in the same neighborhood you did as a child, since they're closed to you if you don't live there any more, (thus guaranteeing Those People South of Us are kept out), you might live in Michigan.
46. If you think, judging from the way your neighbors behave, that Thomas Paine said "Give me librium or give me meth!", you might live in Michigan.
47. If 80% of your childhood friends who graduated from college live in other states now and have never been back, you might live in Michigan.
48. If most factories you drive by have had empty parking lots for more than a decade, you might live in Michigan.
49. If racial hostility is the underlying theme of everyone's politeness to one another, you might live in Michigan.
....you might still live in Michigan.


This entry was posted in Child Category III, Parent Category III and tagged tag1, tag3, tag6 on September 17, 2008 by admin.
This entry was posted in Parent Category II, Parent Category III and tagged tag2, tag4, tag7 on September 11, 2008 by admin.
This entry was posted in Child Category III, Parent Category III and tagged tag1, tag2, tag3, tag5 on September 11, 2008 by admin.


In taking his first double race win of the season at Imola today Jonathan Rea (KRT) made WorldSBK history by equalling the all-time record of 59 career race wins. He now shares that honour with WorldSBK legend Carl Fogarty. Tom Sykes (KRT) finished a fighting third in race two, after sharing a third row starting position with Rea.


Welcome to our First Time Visitors at The Pattern Cupboard!
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The Pattern Cupboard is one of the few Pattern sites online that does not require you to create an Account to place an order and retrieve your Instant Downloadable items. We know how annoying it can be to try to keep track of multiple accounts and passwords, and we like to make the ordering process at The Pattern Cupboard as easy as possible for everyone.
Our Registration feature, should you choose to use it, simply allows you to enter basic personal information, such as your name, physical mailing address, email address, phone and fax, so it will be easier for you to place orders each time you visit. If you plan to visit and shop with us often, it is a quick time saver to fill out our Registration form.
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We hope you have a pleasant Shopping experience and invite you to visit often with us!


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Na mitologia grega, Ismênia (em grego moderno Ισμήνη) era irmã de Antígona, Polinice e Etéocles, filhos incestuosos de Édipo e da rainha Jocasta. Em uma outra versão, a mãe dos filhos de Édipo se chamava Eurygania, filha de Hyperphas.

Era uma mulher frágil, ao contrário da irmã. Ficou triste com a partida de seu pai de Tebas, mas não tomou atitude nenhuma em relação a isso. Quando Creonte lavrou um decreto que proibia qualquer Tebano de enterrar o corpo de Polinice, morto na guerra contra Tebas, Antígona acabou desobedecendo a lei, e enterrando o irmão de ambas. Ismênia tentando defendê-la, tentou levar a culpa e ser morta no lugar da irmã, mas foi logo desmentida pela mesma.

Princesas da mitologia grega


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Wicked Horror Show
The "Wicked Horror Show" is where we interview horror celebrities and indie filmmakers. Recently we've had the likes of Kane Hodder, Dee Wallace, Sid Haig, Barbara Crampton, Lloyd Kaufman and many others. The show is produced LIVE in front of an online audience where viewers can ask questions to our guests.Read more »
The "Wicked Horror Show" is where we interview horror celebrities and indie filmmakers. Recently we've had the likes of Kane Hodder, Dee Wallace, Sid Haig, Barbara Crampton, Lloyd Kaufman and many others. The show is produced LIVE in front of an online audience where viewers can ask questions to our guests.
@thedorkening
/thedorkening
Wicked Horror Show presents: Plaguers 10th anniversary episode with Brad and Josephina Sykes
Brad and Josephina Sykes, the filmmakers behind the cult-classic sci-fi horror release PLAGUERS starring Steve Railsback, are with us tonight to celebrate the film's 10tth anniversary. Deadly Grounds Coffee "Its good to get a little Deadly" https://deadlygroundscoffee.com When a band of sexy space pirates hijack a fuel-transport vessel bound for Earth, an alien virus known only as "Thanatos" is accidentally released. The contagion mutates its victims, transforming them one after another into ravenous, demonic creatures. Pirates and crew must join together to destroy the undead PLAGUERS as the ship nears Earth, threatening to infect the entire planet. Wild Eye Releasing has re-issued the film on Blu-ray and DVD, complete with new extras, to celebrate the release. Brad Sykes is an award-winning filmmaker and author based in Los Angeles. During high school, he wrote and directed multiple shorts (one of which won the top prize in a PBS-sponsored competition) and features on video before attending Boston University's film program, where he graduated cum laude. After moving to Los Angeles and working in studio production and development, Sykes made his feature debut with the horror comedy Scream Queen, starring genre icon Linnea Quigley. Sykes has since written and directed over twenty feature films, including the first digital 3D horror movie, Camp Blood. Camp Blood was a worldwide success and has become one of the longest running franchises in indie horror, with its first two sequels (Camp Blood 2 and Within the Woods aka Camp Blood 3) also written and directed by Sykes. Sykes' film Death Factory became its distributor's all-time top-grossing title and was also later sequelized. Sykes' other writing-directing credits include Goth, Mad Jack, Demon's Kiss, Plaguers (winner Best Screenplay at the 2008 Estepona Film Festival and Best Actor Steve Railsback at 2008 Shockerfest) and Hi-8: Horror Independent Eight, an award-winning horror anthology called "The Expendables of SOV Horror" by HorrorHound. He also co-executive produced Burying the Ex, the new Joe Dante film starring Anton Yelchin and Alexandra Daddario. Sykes' films continue to stream on cable and VOD and enjoy releases on DVD/Blu Ray around the world. They have also received attention in publications including Entertainment Weekly, The Hollywood Reporter, The Dark Side, Sight and Sound, Gorezone and LA Weekly and books such as "Jumpstart Your Awesome Film Production Company", "The Mammoth Book of Slasher Movies", "Horror!: The Definitive Companion to the Most Terrifying Movies Ever Made", and "Horror Films by Subgenre". Sykes has taught film production at the International School of Motion Pictures and has also penned articles for periodicals including Fangoria, Indie Slate and Evilspeak. He currently lives in Los Angeles with his wife, Producer Josephina Sykes, where they operate Nightfall Pictures, a full-service development and production company. Recently, Sykes co-executive produced...
Brad and Josephina Sykes, the filmmakers behind the cult-classic sci-fi horror release PLAGUERS starring Steve Railsback, are with us tonight to celebrate the film's 10tth anniversary. Deadly Grounds Coffee "Its good to get a little Deadly" https://deadlygroundscoffee.com When a band of sexy space pirates hijack a fuel-transport vessel bound for Earth, an alien virus known only as "Thanatos" is accidentally released. The contagion mutates its victims, transforming them one after another into ravenous, demonic creatures. Pirates and crew must join together to destroy the undead PLAGUERS as the ship nears Earth, threatening to infect the entire planet. Wild Eye Releasing has re-issued the film on Blu-ray and DVD, complete with new extras, to celebrate the release. Brad Sykes is an award-winning filmmaker and author based in Los Angeles. During high school, he wrote and directed multiple shorts (one of which won the top prize in a PBS-sponsored competition) and features on video before attending Boston University's film program, where he graduated cum laude. After moving to Los Angeles and working in studio production and development, Sykes made his feature debut with the horror comedy Scream Queen, starring genre icon Linnea Quigley. Sykes has since written and directed over twenty feature films, including the first digital 3D horror movie, Camp Blood. Camp Blood was a worldwide success and has become one of the longest running franchises in indie horror, with its first two sequels (Camp Blood 2 and Within the Woods aka Camp Blood 3) also written and directed by Sykes. Sykes' film Death Factory became its distributor's all-time top-grossing title and was also later sequelized. Sykes' other writing-directing credits include Goth, Mad Jack, Demon's Kiss, Plaguers (winner Best Screenplay at the 2008 Estepona Film Festival and Best Actor Steve Railsback at 2008 Shockerfest) and Hi-8: Horror Independent Eight, an award-winning horror anthology called "The Expendables of SOV Horror" by HorrorHound. He also co-executive produced Burying the Ex, the new Joe Dante film starring Anton Yelchin and Alexandra Daddario. Sykes' films continue to stream on cable and VOD and enjoy releases on DVD/Blu Ray around the world. They have also received attention in publications including Entertainment Weekly, The Hollywood Reporter, The Dark Side, Sight and Sound, Gorezone and LA Weekly and books such as "Jumpstart Your Awesome Film Production Company", "The Mammoth Book of Slasher Movies", "Horror!: The Definitive Companion to the Most Terrifying Movies Ever Made", and "Horror Films by Subgenre". Sykes has taught film production at the International School of Motion Pictures and has also penned articles for periodicals including Fangoria, Indie Slate and Evilspeak. He currently lives in Los Angeles with his wife, Producer Josephina Sykes, where they operate Nightfall Pictures, a full-service development and production company. Recently, Sykes co-executive produced...Read less
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redpajama_set_name: RedPajamaCommonCrawl


text:
The School for Good and Evil: The School for Good and Evil Series
by Soman Chainani
Book one of The School for Good and Evil series.
Sophie had waited all her life to be kidnapped.
Every four years two children are stolen away from Gavaldon, never to return. Most children fear being taken away to the School for Good and Evil. But not Sophie…
She has dreamt all her life of being a princess and believes the school could be her chance.
Her best friend Agatha has other ideas.
When the two girls are taken, things don't go quite to Sophie's plan.
Because sometimes, the princess and the witch don't look like they do in fairy tales.
Posts about The School for Good and Evil: The School for Good and Evil Series


text:
\section{Introduction}

Charge transfer (CT) reactions are of fundamental and broad importance
in chemistry, biochemistry, and materials science \cite{Marcus1985,Bixon1999}.
The CT rate and mechanism are determined by diagonal site energies and off-diagonal transfer integrals
of the Hamiltonian matrix,
which are thus key to elucidating and potentially controlling the reaction \cite{Coropceanu2007,Grozema2008}.

For quantitative evaluation of the Hamiltonian matrix elements,
the effects of orbital relaxation and electron correlation can be significant.
The state-of-the-art wave function approaches such as
the multi-reference configuration-interaction
and
the coupled-cluster
methods
are still computationally expensive \cite{Pieniazek07}, especially for combining with
molecular dynamics simulations \cite{Oberhofer12}.
In this regard, the recently emerging long-range corrected (LC) density functional theory (DFT)
is attractive,
as it takes an improved account of the CT interaction by reducing the self-interaction error
in DFT while maintaining the short-range dynamic correlation effects \cite{Iikura2001,Tawada2004}.
This aspect
on the redox site energies
has been examined recently by
a \lq nonempirically tuned range-separated (NET RS)\rq\ DFT \cite{Foster2012},
in which the range-separation parameter
for decomposing the two-electron Coulomb interaction
is optimized in accord with Janak's theorem
to reproduce
the ionization potential (IP) and electron affinity
by the orbital energies of highest-occupied (HO) and lowest-unoccupied
Kohn-Sham (KS)
molecular orbitals (MOs) \cite{Stein2009}.
The optimal parameters for the nucleobases of DNA and RNA have been thus reported \cite{Foster2012}.

However,
the parameters optimal for the intramolecular site energies are
not necessarily equally appropriate for
the off-diagonal intermolecular transfer integrals.
Nonetheless,
we know empirically that the off-diagonal energies are approximated by the
average of diagonal energies multiplied by the overlap integral and an empirical factor,
as known prototypically for the extended H{\"u}ckel method.
In addition,
the one-electron mean-field picture has been considered appropriate
for the transfer integrals
\cite{Newton80,Yang06,Nishioka11a}
due to cancelation of
the dynamic electron-correlation effect, as the transfer integrals
correspond to the difference between
the energies of two adiabatic electronic states at the diabatic surface crossing.
These aspects are thus intriguing for quantitative evaluation.

The method for computing the off-diagonal transfer integrals is not unique:
it depends on the definition of basis states.
This is analogous to the arbitrariness in defining the diabatic states
for non-adiabatic transitions \cite{Pacher88,Ando94,Subotnik2008}.
When the redox sites or moieties are spatially well-defined,
as is the case for the $\pi$-stack DNA nucleobases,
the MOs of isolated fragments provide a reasonable choice,
as employed in the conventional fragment-orbital approaches \cite{Troisi2001,Senthilkumar2005,Kubar2008}.
However,
the MOs optimized for isolated fragments lack the orbital relaxation
induced by the long-range Coulomb and short-range exchange interactions.
If we are to include these interactions, we need to handle large systems
and have to determine the procedure for transforming
the resulting delocalized canonical MOs to localized diabatic bases.
Thus, there exists a practical trade-off
between the inclusion of orbital relaxation
and the diabatization.
The methods of constrained DFT \cite{QinWu06,delaLande10}
and frozen density embedding \cite{Pavanello13}
are recently proposed prescriptions to this problem.

In this work we put forward another solution by employing
the method of fragment molecular orbitals (FMO) \cite{Kitaura1999, Nakano2002, Fedorov2007,Tanaka2014}
and their linear combinations (FMO-LCMO) \cite{Tsuneyuki2009,Kobori2013,Nishioka2011,Kitoh-Nishioka2012}.
The FMO-LCMO method was originally proposed to obtain canonical MOs of large systems \cite{Tsuneyuki2009,Kobori2013}.
The FMO method first decomposes the total system into fragments
and optimizes the MOs of each fragment self-consistently under the Coulomb field of other fragments.
Then, dimer, trimer, or tetramer calculations are carried out to take account of the exchange interactions.
In the FMO-LCMO method, the diagonal elements of Hamiltonian matrix of the total system
are computed from
the results of these fragment calculations in a form to remove the excess counting of energy,
whereas the off-diagonal elements are constructed from the dimer or trimer matrices projected to the monomer FMO space.
The total Hamiltonian matrix
is then diagonalized
to find the canonical MOs of the entire system.
Now, it is seen that the Hamiltonian matrix before the diagonalization provides
appropriate diagonal site energies and off-diagonal transfer integrals
for the study of CT reactions.

After formulating this idea in Section \ref{sec:method},
Section \ref{sec:results} presents
an assessment of the scheme on benchmark systems and
numerical applications to $\pi$-stack DNA nucleobases.
Section \ref{sec:conclusion} summarizes and concludes.

\section{Method}
\label{sec:method}

Here we outline the FMO-LCMO method \cite{Tsuneyuki2009,Kobori2013,Nishioka2011,Kitoh-Nishioka2012}.
For simplicity, we restrict to the FMO2 version with dimer exchange,
although extension to the trimer FMO3 is straightforward \cite{Kobori2013}.
In the FMO2 method, the orbitals of each fragment are optimized
self-consistently under the Coulomb field of other fragments.
The resultant $p$th orbital of fragment $I$ is denoted by
$\varphi_{p}^{I}$.
The fragment dimer calculations are then carried out under the
Coulomb field of other monomer fragments determined above.
In the FMO-LCMO method, the intra- and inter-fragment Hamiltonian matrix elements
are defined by
\begin{align}
H^{\rm (total)}_{Ip,Iq} &= \sum_{J \ne I}
\langle \varphi_p^I | \ensuremath{\boldsymbol{h}}_{}^{IJ} | \varphi_q^I \rangle
- (N-2)
\langle \varphi_p^I | \ensuremath{\boldsymbol{h}}_{}^{I} | \varphi_q^I \rangle
\label{eq:HtotIpIq}
\\
H^{\rm (total)}_{Ip,Jq} &=
\langle \varphi_p^I | \ensuremath{\boldsymbol{h}}_{}^{IJ} | \varphi_q^J \rangle
\hspace*{1.5em}
(I \ne J),
\label{eq:HtotIpJq}
\end{align}
in which
$\ensuremath{\boldsymbol{h}}_{}^{I}$ and
$\ensuremath{\boldsymbol{h}}_{}^{IJ}$
are the KS (or Fock) matrices of fragment $I$ and fragment dimer $IJ$, respectively.
In Eqs. (\ref{eq:HtotIpIq}) and (\ref{eq:HtotIpJq}),
the notation $\langle \varphi_p^I | \ensuremath{\boldsymbol{h}}_{}^{IJ} | \varphi_q^J \rangle$
represents the dimer KS matrix projected to the monomer orbital space.
The diagonalization of this $H^{\rm (total)}$
has been demonstrated to give
accurate approximations to the canonical MOs and MO energies of
large systems \cite{Tsuneyuki2009,Kobori2013,Nishioka2011,Kitoh-Nishioka2012}.

The proposal in this work is to employ
the matrix elements of $H^{\rm (total)}$
for the orbital site energies $\varepsilon_{Ip}$
and the transfer integrals $T_{Ip,Jq}$ of CT systems.
As seen from the procedure described above,
they include the orbital relaxation from the self-consistent Coulomb field
and the pairwise exchange interactions.
This can be an advantage over methods that employ orbitals optimized for isolated fragments.

Because the orbitals of different fragments are optimized separately in the FMO method,
they are in general non-orthogonal
with finite overlaps
$S_{Ip,Jq} \equiv \langle \varphi_p^I | \varphi_q^J \rangle \ne 0$ for $I \ne J$.
Thus, the transfer integrals appropriate for description of CT processes are
\begin{align}
T_{Ip,Jq}' =
(
H^{\rm (total)}_{Ip,Jq}
- S_{Ip,Jq} ( H^{\rm (total)}_{Ip,Ip}
 + H^{\rm (total)} _{Jq,Jq} ) / 2
)
\nonumber \\
/(1 - S_{Ip,Jq}^2)
\nonumber \\
 = (
T_{Ip,Jq} - S_{Ip,Jq} \left( \varepsilon_{Ip}
 + \varepsilon_{Jq} ) / 2
\right)/(1 - S_{Ip,Jq}^2)
,
\label{eq:Tprime}
\end{align}
from symmetric-orthogonalized orbitals \cite{Lowdin1950}.

In what follows, we will compare the FMO-LCMO with the
fragment-orbital approach (FOA) \cite{Troisi2001,Senthilkumar2005,Kubar2008}
and the generalized Mulliken-Hush (GMH) method \cite{Cave97}.
Both FOA and GMH
have been often employed and well documented in the literature \cite{Kitoh-Nishioka2012,Felix2011,Blancafort2006,Valeev2006}.
However, we outline them below for convenience.

In the FOA,
the orbitals $\phi_i$ are first optimized for isolated monomers.
Next,
the KS matrix of aimed complex
(a dimer or larger assembly of fragment monomers),
$\ensuremath{\boldsymbol{h}}_{\rm KS}^{\rm (cmplx)}$, is constructed
with or without orbital optimization.
The site energies $\varepsilon_i$ and transfer integrals $T_{ij}$ are then
computed with
\begin{align}
\varepsilon_i &=
\langle \phi_i | \ensuremath{\boldsymbol{h}}_{\rm KS}^{\rm (cmplx)} | \phi_i \rangle
\label{eq:FOAsiteE}
\\
T_{ij} &=
\langle \phi_i | \ensuremath{\boldsymbol{h}}_{\rm KS}^{\rm (cmplx)} | \phi_j \rangle
\label{eq:FOATij}
\end{align}
Because the orbitals of different fragments are not orthogonal,
similarly to the case of FMO-LCMO noted above,
the transfer integrals $T'_{ij}$ are computed with the formula
equivalent to Eq. (\ref{eq:Tprime}).

In the GMH method for hole transfers with a one-electron KS-MO approach \cite{Felix2011},
the transfer integral $T'_{ij}$
is approximated by the HOMO (H) and HOMO-1 (M) energy difference for the
neutral dimer fragment of sites $i$ and $j$,
scaled by the dipole moment matrix elements with respect to the two MOs as
\begin{equation}
T'_{ij} =
\frac{( \varepsilon_{\rm H}^{\rm (dim)} -
 \varepsilon_{\rm M}^{\rm (dim)} )
| \mu_{\rm H, M} |}
{\sqrt{(\mu_{\rm H, H} - \mu_{\rm M, M} )^2 +
4 ( \mu_{\rm H, M} )^2}},
\end{equation}
\begin{align}
\mu_{\rm H, M} &=
-\sum_{\alpha \beta } C_{\alpha, \rm H}^{\rm (dim)}
C_{\beta, \rm M}^{\rm (dim)}
d_{\alpha \beta},
\\
\mu_{\rm H, H} - \mu_{\rm M, M} &=
\sum_{\alpha \beta } (  C_{\alpha, \rm H}^{\rm (dim)}
C_{\beta, \rm H}^{\rm (dim)} -
C_{\alpha, \rm M}^{\rm (dim)} C_{\beta, \rm M}^{\rm (dim)}
)
d_{\alpha \beta}.
\end{align}
Here, $C_{\alpha, \rm H}^{\rm (dim)}$
and $C_{\alpha, \rm M}^{\rm (dim)}$ are
the MO coefficients for the dimer fragment
in the atomic orbital (AO) representation and
$d_{\alpha \beta}$ are the dipole matrix element between
the AOs $\alpha$ and $\beta$.

All electronic calculations in this Letter were performed
on neutral monomers, dimers, and octomers using the GAMESS program \cite{Schmidt1993}.

\begin{figure*}
\begin{center}
\includegraphics[width=0.35\textwidth]{./fig1a.pdf}
\includegraphics[width=0.35\textwidth]{./fig1b.pdf}
\end{center}
\caption{
Transfer integrals for (a) imidazole and (b) furane homo-dimer cations
compared with the high-level \textit{ab initio} references \cite{Kubas2014}.
In both (a) and (b), FMO-LCMO and FOA with the same functional almost completely overlap.
}
\end{figure*}

\section{Results and discussion}
\label{sec:results}

\subsection{Assessment on benchmarks: imidazole and furane homo-dimer cations}

We first assess the
nonempirically tuned range-separated (NET RS) functional
for transfer integrals.
The reference data are taken from
a benchmark database \cite{Kubas2014}
with high-level \textit{ab initio} calculations
of multireference configuration interaction (MRCI+Q) and
$n$-electron valence state perturbation theory (NEVPT2).
From the database we have chosen imidazole and furane homo-dimer cations
because their molecular structures are most related to the nucleobases.

The optimal values of range-separation parameter $\mu$
in the formula
\(
{1}/{r_{12}} = (1 - {\rm erf} ( \mu r_{12}))/{r_{12}} + {\rm erf} ( \mu r_{12})/{r_{12}}
\)
with the LC-Becke\cite{Becke1988}-Lee-Yang-Parr\cite{Lee1988} (LC-BLYP) functional \cite{Tawada2004}
for imidazole and furane monomers
were searched
with the procedure described in Ref. \cite{Foster2012},
and were found to be $\mu = 0.33$ bohr$^{-1}$ for both molecules.
Here we used the cc-pVTZ basis set for heavy atoms and cc-pVDZ for hydrogens,
although Ref. \cite{Kubas2014} employed
aug-cc-pVTZ for the former.
However, the results displayed in Figure 1 present high accuracy.
By contrast, the standard B3LYP functional \cite{Becke1993}
systematically underestimates the transfer integrals
for both systems.
The figure also indicate that the results from FMO-LCMO and FOA
with the same functional are almost identical.
The numerical values are listed in Table S1 of the Supplementary materials.

\begin{figure}
\begin{center}
\includegraphics[width=0.35\textwidth]{./fig2.pdf}
\end{center}
\caption{
HOMO energies with LC-BLYP functional and experimental IPs
of four nucleobases, guanine (G), adenine (A), cytosine (C), and thymine (T).
Each experimental IP has an uncertainty of $\pm 0.1$ eV.
}
\end{figure}

\begin{figure*}
\begin{center}
\includegraphics[width=0.35\textwidth]{./fig3a.pdf}
\includegraphics[width=0.35\textwidth]{./fig3b.pdf}
\end{center}
\caption{
Adiabatic energy gaps $\Delta E'_{ij}$ (a) and hole-transfer integral $|T'_{ij}|$ (b)
of nucleobase pairs GG, GA, AG, GT, TG,
with 6-31G(d) basis-set.
In (b), \lq $\mu$-alt\rq\ refers to a GMH calculation with the energy gap from CASPT2
and the dipole moment matrix elements from LC-BLYP.
In (a), FMO-LCMO and FOA with the same functional almost completely overlap.
In (b),
FMO-LCMO and GMH overlap for AG, GT, and TG
for both functionals.
}
\end{figure*}

\subsection{Isolated nucleobases with a single range-separation parameter}

We now proceed to the nucleobase molecules.
The optimal values of the parameter $\mu$
with the LC-BLYP functional
and cc-pVTZ basis set have been reported (in bohr$^{-1}$) as
0.2738 for guanine (G),
0.2853 for adenine (A),
0.2948 for cytosine (C),
and
0.2850 for thymine (T) \cite{Foster2012}.
These were optimized separately for each nucleobase.
However,
we need to determine a single value for the computation of intermolecular transfer integrals,
for which we have chosen $\mu = 0.29$
because the latter three nucleobases have approximately this value.
With this we then reexamined the site energies.
The nuclear coordinates are taken from Ref. \cite{Foster2012}.

The resultant HOMO-1 and HOMO energies
are displayed in Figure 2.
They are compared with those from the original optimal $\mu$ for each nucleobase and
with the corresponding experimental IPs \cite{Faber2011}.
The numerical values are listed in Table S2 of the Supplementary materials.
We see that the parameter $\mu = 0.29$
yields the orbital energies sufficiently close to those
with the optimal $\mu$ for each nucleobase.
We have also carried out calculations with 6-31G(d) basis set
in an aim to compare with the previous works \cite{Felix2011, Blancafort2006},
which will be discussed in Section \ref{subsec:basepair}.
Although the 6-31G(d) basis set systematically underestimate the absolute values,
the relative HOMO energies among the nucleobases,
the most relevant quantities for the hole transfers,
indicated by the slope of the plots
are similar among the methods and the experiment.
Having in scope the calculations of larger systems, it is desired to keep the size
of basis-set as small as possible.
We thus employ the 6-31G(d) basis-set
hereafter, until we examine the basis-set dependence in Section \ref{subsec:basisEffect}.

\subsection{Hole transfer integrals for nucleobase pairs}
\label{subsec:basepair}

Here we examine the CT energies for nucleobase pairs in a $\pi$-stack configuration.
As guanine is the key donor with the lowest IP, we study
GG, GA, AG, GT, and TG pairs.
The nuclear coordinates are taken from Ref. \cite{Blancafort2006}.
Because the reference data from CASPT2 calculation \cite{Blancafort2006}
corresponds to
the adiabatic energy gap
rather than the diabatic site energy difference,
we have also calculated the adiabatic energy gaps from the diabatic site energies and
the transfer integrals.
The numerical values are listed in Table S3 of the Supplementary materials.

The resultant adiabatic energy gaps and transfer integrals are
plotted in Figure 3
for the LC-BLYP functional with $\mu = 0.29$ compared to B3LYP
and CASPT2.
Figure 3a indicates that
the adiabatic energy gaps from LC-BLYP are closer to CASPT2.
We also see that the values from FMO-LCMO and FOA with the same functional coincide
well to be indistinguishable in the figure;
the difference is approximately 1 meV as seen in Table S3.
The difference between FMO-LCMO and FOA is
in the treatment of orbital relaxation of the basis MOs.
It is included in the former while not in the latter.
This effect is more apparent in the transfer integrals discussed next.

Figure 3b compares the transfer integrals $T'$.
For both LC-BLYP and B3LYP functionals,
FMO-LCMO and GMH coincide well
for AG, GT, and TG.
Notably, their deviation from FOA is now apparent.
This is due to the effect of orbital relaxation
that is included in GMH and FMO-LCMO but not in FOA.
The numerical values of the transfer integrals are listed in Table S4 of the Supplementary materials.

Figure 3b also indicates that the transfer integrals from CASPT2 notably deviate
from both LC-BLYP and B3LYP.
Considering the accuracy of LC-BLYP confirmed in Figure 1
and the limited active orbital space
employed in the CASPT2 \cite{Blancafort2006},
we have tested a GMH calculation with the energy gap from CASPT2
and the dipole moment matrix elements from LC-BLYP.
The results denoted by \lq $\mu$-alt\rq\ in Figure 3b
are now close to LC-BLYP.
It would be plausible that the limited CASPT2 calculations
yield more reliable energy gaps than dipole matrix elements.
We also note in Figure 3b that B3LYP underestimates the transfer integrals for
all the nucleobase pairs, the same tendency as was observed in Figure 1.

\begin{figure}
\begin{center}
\includegraphics[height=0.3\textheight]{./fig4.pdf}
\end{center}
\caption{
Structure of adenine octomer in the
idealized B-DNA $\pi$-stack configuration.
}
\end{figure}

\subsection{$\pi$-Stack adenine molecules}
\label{subsec:adenines}

Next, we study a larger system, an adenine octomer in the
idealized B-DNA $\pi$-stack configuration (Figure 4).
The structure of atoms other than hydrogen are constructed
by using the Web-3DNA software \cite{Zheng2009}.
The positions of hydrogen atoms are optimized for each isolated adenine
by B3LYP/6-31G(d) calculation.

As discussed above,
one major difference between FOA and FMO-LCMO is in the treatment of orbital relaxation.
Another difference is in the scaling of computational cost along the system size.
In the standard use of FOA,
the basis MOs are computed for each isolated monomer of donor and acceptor molecules.
Then, the KS matrix of the entire donor-acceptor system is constructed,
over which the matrix elements on the basis MOs from the monomer calculation
are computed (see Eqs. (\ref{eq:FOAsiteE}) and (\ref{eq:FOATij})).
Therefore, to study the system of Figure 4, for instance,
the full KS matrix
$ \ensuremath{\boldsymbol{h}}_{\rm KS}^{\rm (total)}$ of the entire eight molecules should be calculated.
This
will quickly become
computationally prohibitive as the system size increases.

An evasion of
this size-scaling problem in FOA
would be to reduce the size of KS matrix to the dimer
$ \ensuremath{\boldsymbol{h}}_{\rm KS}^{\rm (dim)}$
for each donor-acceptor pair.
In such cases,
in order to take account of the orbital relaxation, the calculations may be performed
under the classical electrostatic, or the \lq molecular-mechanical (MM)\rq,
field from the other molecules. \cite{Ando94,Kubar2008,Valeev2006}
We thus first determine the
effective atomic charges
derived from the electrostatic potential (ESP) of an isolated alanine monomer,
in which both the structure and MOs are computed at the B3LYP/6-31G(d) level.
The results displayed in Figure S1 of the Supplementary materials
indicate that they are consistent with the AMBER 94 force-field \cite{Cornell1995}.

We now compute the basis MOs of each monomer in Figure 4
under the classical field from the
ESP charges of others.
The KS matrix of donor-acceptor pairs are similarly computed under the classical
field of remaining molecules.
This procedure is denoted by \lq Dimer in MM\rq.
The ordinary FOA without the MM field is denoted by \lq Dimer in Vac(uum)\rq.
These methods are summarized in Table 1 with respect to the orbital relaxation
effect in the basis MOs and the KS matrix.

\begin{table*}
Table 1.
Orbital relaxation in different computational schemes.
\\[1em]
\setlength{\tabcolsep}{1.5em}
\begin{tabular}{lllllll}
\hline \hline
          & {FMO-LCMO} &  Full FOA & \multicolumn{2}{c}{Dimer in MM} & \multicolumn{2}{c}{Dimer in Vac} \\
\cline{4-5}
\cline{6-7}
Orbital relaxation     &             &           &  FOA            &  GMH$^{c}$ &  FOA   &  GMH   \\
\hline
Basis MOs              &  Yes        &  No       &  MM$^{a}$       &  ---       &  No    &  ---   \\
KS matrix              &  Yes        &  Yes      &  MM+dimer$^{b}$ &  MM+dimer  &  Dimer &  Dimer \\
\hline \hline
\end{tabular}
\\[1em]
{}$^{a}$ The orbital relaxation is included via the MM field of point charges.
\\
{}$^{b}$ The orbital relaxation is included in the dimer calculation.
\\
{}$^{c}$
GMH computes the transfer integral from the dipole matrix and does not involve
the \lq basis MOs\rq.
\end{table*}

\begin{figure}
\begin{center}
\includegraphics[width=0.35\textwidth]{./fig5a.pdf}
\includegraphics[width=0.35\textwidth]{./fig5b.pdf}
\end{center}
\caption{
Site energies and their differences in the adenine octomer
with 6-31G(d) basis-set.
}
\end{figure}

Figure 5 plots the site energies
of each adenine molecule and their differences $\Delta E_{ij}$ in the adjacent pairs.
The numerical values are listed in Table S5 of the Supplementary materials.
Figure 5a indicates that the site energies by the \lq Dimer in Vac\rq\ method
are almost independent of the position,
naturally because the pairs are treated independently.
We also see that the absolute site energies are notably overestimated in the isolated pairs.
Contrastingly,
the maximum of
the site energy near the middle of the chain A4-A5
is qualitatively captured by
the \lq Dimer in MM\rq\ method,
although the absolute energies are generally underestimated by approximately 0.1 eV.
Finally, we note that the site energies by the FMO-LCMO and the full FOA are consistent,
while the computational cost is notably reduced in the former.
Figure 5b indicates that the cancelation of errors in the site energies
from the \lq Dimer in MM\rq\ method
results in correct profile of the site energy difference $\Delta E_{ij}$,
particularly in the region excluding the pairs at both ends of the chain.

\begin{figure}
\begin{center}
\includegraphics[width=0.35\textwidth]{./fig6.pdf}
\end{center}
\caption{
Transfer integrals between the adenine octomer
with 6-31G(d) basis-set.
}
\end{figure}

Figure 6 plots the transfer integrals $T'_{ij}$ between the HOMOs of adjacent adenine molecules.
The numerical values are listed in Table S6 of the Supplementary materials.
We first note that the results obtained from full FOA and
FOA with \lq Dimer in MM\rq\ coincide well,
with the exceptions in the A1/A2 and A7/A8 pairs at both ends.
To these two curves, that of FOA with \lq Dimer in Vac\rq\ is nearly parallel.
The same applies to the GMH with \lq Dimer in Vac\rq,
although the quantitative values are overestimated.
The profile of FMO-LCMO is overall different,
which is similar to that of
GMH with \lq Dimer in MM\rq.
The differences are most significant at both ends, A1/A2 and A7/A8,
which may be comprehended in terms of the balance between the
inclusion of orbital relaxation effects in the basis MOs and in the KS matrix,
as presented in Table 1.

\subsection{Dependence on the basis-set}
\label{subsec:basisEffect}

\begin{figure*}
\begin{center}
\includegraphics[width=0.35\textwidth]{./fig7a.pdf}
\includegraphics[width=0.35\textwidth]{./fig7b.pdf}
\end{center}
\caption{
Comparison between 6-31G(d) and cc-pVTZ basis-sets for the
(a) site energy differences and (b) transfer integrals in the adenine octomer.
In (b), the values from 6-31G(d) basis-set
were shifted by +10 meV for better view (see Figure 6).
}
\end{figure*}

Finally, we confirm that the pictures obtained in the previous sections
are basically independent of the size of the basis-set.
Figure 7 compares between 6-31G(d) and cc-pVTZ basis-sets for the
site energy differences and the transfer integrals.
The numerical values are listed in Table S7 of the Supplementary materials.
Note that the values from 6-31G(d) are shifted by +10 meV in Figure 7b
for better view.
Except this quantitative shift, the overall qualitative behavior is mostly
identical between the two basis-sets.
Therefore, the use of 6-31G(d) can be recommended
for major part of studies,
with additional quantitative corrections
with larger basis-sets,
for instance,
at selected key configurations
according to specific necessities.

\section{Conclusion}
\label{sec:conclusion}

A scheme for computing CT energies with a combination of the FMO-LCMO method
and the NET RS DFT
was proposed, assessed on the benchmark systems of imidazole and furane
homo-dimer cations,
and applied to hole transfers in DNA nucleobases.
The NET RS
functional optimized for intramolecular site energies
was found to give the intermolecular CT integrals
notably close
to the MRCI+Q and NEVPT2 references.
In the applications to nucleaobases,
the FMO-LCMO gave the CT energies
comparable to those with the full FOA
at lower computational cost:
the efficiency will become more prominent as the system size increases.
The use of classical point charges to remedy the lack of orbital relaxation
in the dimer FOA calculations gave reasonable results
due to the cancelation of errors
in the site energy differences and transfer integrals.
Further details in the computational schemes were investigated in terms of
the orbital relaxation effect.

We have chosen to examine the hole transfer integrals of DNA nucleobases
partly because of their own importance
and partly in an aim to compare with the previous works.
However, the proposed combination of FMO-LCMO and NET RS DFT
will be more effective
in broad cases where the orbital relaxation and the exchange interactions are more significant.
For instance, when interactions with solvent and counter ions are involved,
the classical point-charge approximation will be less appropriate, particularly
when their configurations thermally fluctuate.
This will come out crucial
when positive classical charges
without the short-range exchange repulsion
overly attract the electrons.
Studies on such cases will be reported in due course.

\section*{Acknowledgments}

The authors acknowledge support from KAKENHI Nos. 20108017 (``$\pi$-space'') and 22550012.
H. K.-N. also acknowledges support from Collaborative Research Program for Young Scientists
of ACCMS and IIMC, Kyoto University.

redpajama_set_name: RedPajamaArXiv


text:
Chrissy Teigen Fights Instagram By Posting Nude Picture
Trending News: Supermodel Chrissy Teigen Just Posted A Nude Photo On Instagram
Because when attractive people argue over the rules of instagram, we all win.
the nipple has been temporarily silenced but she will be back, oh yes, she will be back
— christine teigen (@chrissyteigen) June 29, 2015
Model and TV personality Chrissy Teigen posted a photo of herself Monday with her nipple exposed, which violates Instagram's terms of service. It's not the first time she's broken the rules, either.
Chrissy Teigen is many things — a model, a TV personality, an entertaining Twitter user and John Legend's wife. Now, she can add another item to that list: Instagram rabble rouser. On Monday, Chrissy posted a picture of herself to Instagram that features — God forbid — one whole nipple (NSFW):
The image comes from a photoshoot for W magazine, where Teigen was named one of the sexiest supermodels on social media. She's joined by Emily Ratajkowski, Joan Smalls, Rosie Huntington-Whiteley, Irina Shayk, Lily Aldridge, Bella Hadid, Anna Ewers, Barbara Palvin and Doutzen Kroes. Chrissy, however, was the only one who didn't have any need for clothes.
"The most uncomfortable I've ever been on set was having to model coats. I actually am better in less clothing," she said in the article.
This isn't the first time a celebrity has run afoul of Instagram's nudity rules, nor is it the first time Chrissy Teigen has done so. Last year, Chelsea Handler famously continued to post topless pictures to Instagram, specifically calling attention to what she feels is a hypocritical policy that bans depictions of female nipples, but not male.
But Teigen herself is something of a pioneer in that regard. In 2013, when she'd passed 200,000 followers on Twitter, she Instagrammed a photo of herself totally nude getting a spray tan. Since the photo didn't appear to show any naughty bits, it stayed active for about 12 hours before it was ultimately taken down. Rihanna has experienced similar issues with the popular photo-sharing service.
This time, instagram will surely come around soon enough, but in the mean time: Thank you, Chrissy Teigen.
Ask The Big Question: Is it time for Instagram to loosen up when it comes to this stuff?
Disrupt Your Feed
: Now this is a brand of activism that I can get behind.
Drop This Fact: Teigen's first naughty photo on Instagram racked up over 6,500 likes before it was removed.
Sports Illustrated Models
Should Everyone Really Sleep for 8 Hours a Day? Experts Weigh InRead More
Trending News: Chelsea Handler Gave This XXX Gift To Her Friend Reese Witherspoon
Trending News: Charlotte McKinney Posts Nude Pics To Instagram - But Was She Hacked?
'Naked Philanthropist' Uses Naked Photos to Help Australian Bushfire Relief
Trending News: A Nude Pic Of Sia Was Leaked - Her Response Is A Lesson For Us All


CAIRO, Feb 28 (Reuters) - Egypt's top cigarette maker Eastern Company SAE obtained approval from Egypt's Financial Regulatory Authority to offer an additional 4.5 percent of its shares on the Egyptian stock exchange, a source familiar with the offering said on Thursday.
The private offering to institutional investors of around 95 percent of the offered shares began on Thursday and will end later in the day, the source said.
The public offering for small investors will begin on Sunday and end on Tuesday, the source said.
The indicative price for the offering is between 16.84 and 20.85 Egyptian pounds per share, the source said.
It was to be the first of up to five sales previously due by the end of 2018, but plans were derailed by global market volatility. Another 18 sales were expected over the next few years.


Just a quick on to let you all know im going ok. Just been abit tired and busy with family. I think AF is on her way as Ive got a bit of cramps in the tum. Oh I hope AF stays away but if not im blessed already with 2 beautiful kids.
How you all doing. Hey DW missed you to hun. How you coping???
Wanted - those about to embark on the Two Week Wait!!!
All times are GMT +10. The time now is 07:39 AM.


text:
Royals promote Mark Wallace to VP sales, marketing
PUBLISHED: May 22, 2014 at 1:00 a.m. | UPDATED: August 19, 2021 at 7:23 a.m.
The Reading Royals announced that Mark Wallace has been promoted to the position of vice president of sales and marketing.
Wallace, who is entering his eighth season with the Royals and had been the general manager since 2010, will begin his new role immediately.
"Mark has been a very important part of the Royals' success," team owner Jack Gulati said in a statement. "A key component of our business philosophy is to put the best available persons in roles that allow them to achieve success for themselves and our business. Mark's experience in the sports industry, outgoing personality and long-term relationship with the fans and business community in the Greater Reading Region make him the perfect person to lead our efforts in sales and marketing."
Wallace, 49, originally joined the Sovereign Center and Royals in July 2007 after a four-year stint as the sales and marketing director at Body Zone Sports and Wellness Complex.
Wallace, who holds a masters degree in communications from Clarion University, also was the athletic director for the Wyomissing Area School District, director of communications and community development for the Reading Phillies and sports information director for Albright College.
Edwin Suarez scores career-high 32 to lead Muhlenberg boys past Exeter
Reading Royals continue offensive hot streak in win over Worcester
Antietam's Hector Tiburcio is motivated to win elusive boys basketball title
Kutztown University beats buzzer to defeat West Chester in men's basketball


mydesigns needed a new web page design and created a contest on 99designs.
3 very similar pages (.PSD files), NO CODING REQ'D.
Once one page is done, the others should be very simple to create (i.e. copy/paste).
Our client is an internet service and communications company.
We're overseeing/contracting out the re-design of their web site. We cannot disclose the name of company.
DO NOT USE any existing company logos or names in your design entries. Please just make a placeholder logo, we'll replace with our client's logo later.
PLEASE READ the detailed description and look at the provided images (links on photobucket).
This contest is for the design of 3 pages only (.PSD files), NO CODING REQ'D. We need 3 pages designed: homepage, category page, individual product page. We will use the product and category pages to build out the entire site for our client.
LOGO: NOT REQUIRED. Just put in a placeholder. We'll place our client's logo in the design later.
Small graphics: Please try to keep the graphic file sizes as small as possible. A significant number of our client's site visitors are still using dial-up service. We need the finished web page design and code to load quickly.
Color theme: The background of the body (960px wide) should be white. You can use oranges, blues, greens and grays as needed in the different blocks/sections of the layout. Other colors can be used for bullets or icons, but the main colors should be oranges, blues, greens, grays, and white. The edges (beyond the 960px wide body) can be some other background color (light gray or another light color).
Gradients: The use of gradients on navigation and section header tabs/bars is encouraged.
Navigation Bar: Please just make up text links to use in the navigation bar (i.e. DSL, PHONE SERVICE, TV, etc). We'll replace them with our client's links when we get the site coded up.
Splash (large area at top of a page): Each page will have a splash element at the top of the page that will either be the entire width of the page or ~70% of the width of the page, depending on which page it is (see detailed page requirements below). This splash element will feature a particular service or group of services and will contain the following elements: an image of someone using the service (at the left of the splash), name of product, a small descriptive paragraph, bulleted list of features, some kind of user rating element (i.e. stars), and a large button that says "sign up now" or "start now" or similar.
Please use fotolia.com for stock imagery if you can. You can download comp images for the design. If we like the images, we'll purchase them and use them in the final design delivery to our client.
Design Blocks: Design the pages so that individual products or categories of products are grouped together in block sections on the page. These blocks will include product name, short decriptive paragraph, bullet list of features, learn more and sign up buttons or links.
Here are a few examples of designs we like...they are just for reference. Please don't copy their designs.
Splash Block: The home page will feature a particular service (i.e. DSL High Speed Internet) in the splash element at the top of the page. This splash element will be about 70% of the page width, aligned left on the page. The general elements for a splash (listed above) should be in the homepage splash.
Category Blocks (below the splash): Below the homepage splash please add thin verticle blocks that feature the different service categories. So for example, the client offers serveral different speeds of DSL High Speed Internet (we'd call DSL a category) - one of the blocks on the homepaqe would show a general description of the DSL product category. Another verticle block might show another category of products. In each of these verticle blocks prompt the user to learn more about the category with a link or a button.
Right Side Blocks: On the right hand side of the homepage please include various block elements that might include: newsletter signup form, featured services, ads, blog post snippets, news snippets, latest forum entries, list of articles.
Splash Block: The category page splash will be the entire width of the page. It will feature/highlight one of the products/services in the category. Be sure to include a brief service description, feature bullet points, and 2 buttons "sign up now" and "learn more".
Product Blocks: Below the category page splash, please include individual verticle product/service blocks and include the name of the product, short description, small bulleted feature list, learn more and sign up buttons/links. One of the blocks is the featured service...so please make it stand out from the others (it should be very obvious which of the services is the recommended/featured service). Note that these product/service blocks will only fill up about 70% of the width of the page leaving an area on the right side of the page for featured services, ads, blog article snippets, etc...like on the homepage.
Right Side Blocks: On the right hand side of the homepage please include various block elements that might include: newsletter signup form, featured services, ads, blog article snippets, news snippets, latest forum entries, list of articles.
Articles/News/User Comments/Reviews: Under the category block/areas we need a section for articles, news, user reviews & comments.
Splash Block: The product/service page splash will take up the entire width of the page. It will include an image of someone using the service (i.e. someone using a computer), a short description, a few bullet points explaining the top features, pricing, a "sign up now" or "get started" button.
Product Description: Under the product/service page splash will be a product description block/area. Use icons or other representative images to emphasize the product description paragraphs. You don't know the details of the products/services obviously, so just design with representative graphics that we will replace when the content is created.
- By the way, rounded corners are ok...don't take my block layout design too literally.
- Small graphic elements...the final pages should load quickly (we know that coders play a part in this, but we'd like you to be thinking about it when you design).
- DO NOT use any existing company logos or names - please just make something up. We'll replace your bogus company logo and graphics with our client's when required.


Using adaptive MCMC to update continuous parameters in BEAST.
In phylogenetic analyses, partitioning strategies (for example: by gene, by codon position, or both) involve estimating conditionally independent models of molecular evolution for those partitions, requiring a large number of evolutionary parameters that have to be estimated. This leads to an increased computational burden for such analyses. With the rise of multi-core processors, massively parallel computations can be enabled that are not yet fully exploited by many phylogenetic software packages for multipartite analyses.
The adaptive Metropolis (AM) algorithm is based on the classical random walk Metropolis algorithm (Metropolis et al., 1953) and an earlier study by Haario et al. (1999) that entertains a Gaussian proposal distribution centred on the chain's current state and with a covariance calculated from a fixed number of previous states. The AM algorithm generalizes this by computing the covariance of the proposal distribution using all of the previous states. An important advantage of the AM algorithm is that it starts using the cumulating information from the beginning of the run, ensuring that the search becomes more effective at an early stage.
In essence, an adaptive MCMC approach such as the one presented here attempts to automatically learn optimal parameter values for a collection of parameters by analysing the previous parameter values visited at earlier states of the analysis. As such, adaptive MCMC transition kernels are non-Markovian, as they take into account a possible large collection of previous states to make proposals for the next state in the Markov chain.
This tutorial requires that you have a standard BEAST XML, as for example generated by BEAUti, at the ready. This XML will be modified to replace the default transition kernels by one or more adaptable variance multivariate normal transition kernels. Note that we're in the process of incorporating this functionality into BEAUti.
In other words, the are 3 transition kernels acting upon the κ parameter of each codon position/partition and 3 transition kernels acting upon the α parameter - describing the distribution that models among-site rate heterogeneity. Additionally, the birth rate ψ of the tree prior and the μ parameters - describing the relative rate parameters - are being estimated. Other transition kernels in this example include those that work upon the tree topology and the branch lengths, which at the moment cannot be incorporated into an adaptive MCMC analysis.
The important attributes to set in the adaptable variance multivariate normal operator are the weight, the initial phase of the operator and the burn-in phase of the operators. While the beta and coefficient attributes can be manually set, we recommend leaving those at their default values,which are shown above. To determine the weight of this operator, we have simply summed over all the weights assigned to the default transition kernels shown in the previous section. We recommend a default value of 5000 for the initial phase of this operator, during which no learning is being done by analysing the values of the various parameters so far during the analysis. We also typically set the burn-in phase of the operator at half that value, i.e. 2500 in this example, which represents the amount of parameter values that will not be used for the automatic learning process.
Apart from the compound parameter that needs to be provided to the operator, a number of transformation - corresponding to the parameters included in the operator - need to be provided. Typically, a 'log'-transformation needs to be provided for those parameters with domain [0, +∞], whereas the transformation type 'none' can be used for those parameters with domain [-∞,+∞]. Note that, in this representation, 'start' and 'end' values need to be provided for the transformations (with the first parameters receiving index 1). For example, parameters 1 through 7 - corresponding to 'ND5.CP1.kappa' through 'yule.birthRate' all need to be 'log'-transformed independently from one another.
The transformation type 'logConstrainedSum' should be used for those continuous parameters that sum to a fixed value, such as for example the relative rates between codon positions. This XML specification has since been updated (see the following section), and this old XML specification had the logConstrainedSum-transformation apply only to parameter collections, where the fixed sum is equal to the number of parameters in the collection. For example, in the case of relative rates, the fixed total sum is equal to 3 in the case of partitioning by codon position, and there are 3 relative rate parameters. This means that using this old XML specification, a set of base frequencies that need to be estimated could be included in the adaptive MCMC transition kernel (but see the next section).
Finally, note that it is possible to use multiple adaptable variance multivariate normal operators in a BEAST XML, operating on (not necessarily) different sets of (continuous) parameters. For example, in our paper (Baele et al., 2017) we show the possibility of creating a separate operator for the parameters of the tree prior.
The first XML representation (as used in the XML examples accompanying our paper; Baele et al., 2017) is not very flexible when it comes to dealing with many parameters, each with their own transformation. Additionally, there's the need to construct a compound parameter in the XML file, for specific use with the novel transition kernel. In this section, we present an XML representation of the adaptive MCMC transition kernel that does not require the construction of a compound parameter nor manual derivation of the indices for the transformation. Additionally, for the example presented here, we will also assume that the base frequencies for each codon position will be estimated.
Given that, when using GPUs, the likelihood evaluation of each unique site pattern ends up being evaluated on the same device. Hence, this load-balancing approach is only useful on multi-core CPUs.
G. Baele, P. Lemey, A. Rambaut and M. A. Suchard (2017) Adaptive MCMC in Bayesian phylogenetics: an application to analyzing partitioned data in BEAST. Bioinformatics 33(12): 1798-1805.
N. Metropolis et al. (1953) Equations of state calculations by fast computing machines. J. Chem. Phys, 21, 1087–1091.
H. Haario et al. (2001) An adaptive Metropolis algorithm. Bernouilli, 7, 223–242.


text:
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Cable TV hookups are at your disposal, so you may watch TV, and this is a good location for RV-ing. Going camping here in Missouri is something you must do. If you've got cabin fever from too much time inside, Don't fret; Henry's is a good local campground if you happen to be in Missouri. There's so many things to do at Henry's including swimming, fishing, playing golf, whitewater paddling, and hiking, so almost certainly you want to stay for a while.
to come. Henry's is one of the locations to camp here in the Ozarks.
have folks coming from all over.
Henry's is a campground relatively often visited by the people of Pomona.
is a magnificent place to go to; for you golfers we recommend close by West Plains Municipal Golf. Places like Grand Gulf State Park are magnificent to explore; a day of fishing at Ozark Wings is always an excellent idea.
Outdoors recreation in the vicinity of West Plains, Missouri, the metro area neareast to Henry's. Find info on campgrounds, marinas, hiking trails, ski resorts, lakes, beaches, parks, whitewater, golf courses and more.


It is with great enthusiasm and excitement we announce our 2018-2019 Head Coaches for the 14U-A1 & 16U-A1 teams!
Dustin played Junior "A" hockey for the Penticton Vees from 2005-2007. He then moved up to the Spokane Chiefs in the WHL and won the Memorial Cup in 2008. He finished his Junior career with the Lethbridge Hurricanes in 2010. Donaghy then turned pro with the Allen Americans of the CHL in 2010-2011. Midway through the season, he was traded tot the Wichita Thunder where he played from 2010-2014. Dustin carries his High Performance 1 Certification as well as a USA Hockey Level 3 Certification. Dustin was the Coach for the 16U Midget Varsity team at the CDA Hockey Academy that plays in the CSSHL. Dustin has spent the past 2 seasons as an Assistant Coach in the BCHL Junior "A" Hockey League.
Please see this post for more information on how to register for our 14U-A1/16U-A1 Rep Team evaluations! We're looking forward to a great 2018-19 season.


So it's all illuminating for me nowadays! Why? Because my skin is dry (from stress and lack of sleep) and seriously, looking at my skin condition, I ain't getting any younger for sure! So my choice of blush nowadays are quite unique, I am always on a look out for dual-purpose blush! A blush color + illumination! And I got that from Wet n Wild Mega Glow Illuminating Powder, the shade I got is called Strike-A-Pose-Rose!
Naturally radiant skin is not so difficult to achieve. By using the right make up, one may achieve a natural and youthful look. The Mega Glo Illuminating Powder by Wet N Wild can enhance and improve natural skin tones. This versatile powder can be worn not only on the face but in various parts of the body such as the chest, neck and shoulder blades. For a sun-kissed look, swipe the powder on your cheeks, nose and shoulder blades.
Strike-A-Pose is a perfect "pink blush" for those who feel like a regular matte pink blush is too teenager-looking or fake-looking for them! I personally am not a fan of pink blushes because they look too obvious when worn so the best way is to go for pink blush with iridescence just like this one from Wet N Wild.
Why is this worth every single penny? Aside from the fact that you can use this all over your body as a natural shimmer, you can also use most of the shades as eyeshadow! Just don't forget to pile your lashes with loads of mascara and use your favorite liquid liner to create dimension!
AMW wore Strike-A-Pose-Rose on Cheeks, used the lightest color on my nose bridge and applied a single color of the darkest pink shade on my lid!
The price is indeed worth it! You get multi-tasking product for less than Php500.00. Note though that this powder won't last the whole day so retouching is needed especially if you are on the oily and combination skin side!
The shade is perfect for users who have fair and medium complexion, if you have darker complexion, the "pink" shade won't show up as much but you'll definitely get the glow that I got!
Have you tried Mega Glo Illuminating Powder?
Any other shades you may recommend?
pretty and natural looking ms nikki!
hahah thanks :) I wish everyday!
I think may bagong version na sila nito? Or eto pa rin yun?


text:
var express = require('express')
  , routes = require('./planning/routes.js')
  , http = require('http')
  , path = require('path');

var app = express();

app.configure(function(){
  app.set('port', process.env.PORT || 8088);
  app.set('views', __dirname + '/planning/views');
  app.engine('html', require('ejs').renderFile);
  app.use(express.favicon());
  app.use(express.logger('dev'));
  app.use(express.bodyParser());
  app.use(express.methodOverride());
  app.use(app.router);
  app.use(express.static(path.join(__dirname, 'planning/public')));
});

app.configure('development', function(){
  app.use(express.errorHandler());
});

app.get('/', routes.index);

http.createServer(app).listen(app.get('port'), function(){
  console.log("Express server listening on port " + app.get('port'));
});


Today is the day after Christmas. I heard from unexpected people, and missed hearing from a few I just assumed would get in touch for the holidays. So, I will look in the mailbox each day this week, just in case a late card or note arrives. So will you.
Why? Is it really that important that at least once a year we hear from folks we haven't had contact with for over eleven months? Sure it is, because friends are friends. The very nature of friendship is voluntary caring and mutual respect and pleasure in one another's company.
Unlike family, friendship involves a choice based on sometimes mysterious mental and emotional calculations that cannot be explained. You just really like someone and enjoy their company. Friendships like this can go on for a lifetime or not, but they are very real.
No one likes to feel they are forgotten or have faded into someone else's background, nor does God.
An intriguing Scripture on this subject is Amos 3:3; "Can any two walk together, except they be agreed?" Then, in John 15:14 Jesus states: "You are my friends, if you do whatever I command you." The first Scripture sounds like a mutual admiration society where both parties have willingly decided to walk the same path together at the same rate.
The second implies that one friend is in authority over the other, and they can only walk together if this status remains unchanged. In Amos, God pleads with Israel to come back into agreement with Him and experience His blessing instead of His judgment. In the second, Jesus is addressing His disciples. He doesn't change the nature of friendship with God, but rather makes it personal, establishing it through the grace of forgiveness.
True friendship does not imply perfection in performance, but rather an attitude of love, forgiveness, and willingness to please one another. Jesus became one of us so we might see His love for us, creating in us a desire to know Him personally. He demonstrated His desire to establish a personal and permanent relationship with us through His Cross, His resurrection, and the sending to us of the Holy Spirit.
We may miss hearing from certain friends this year, but one thing is sure, through the Word and Spirit of God, we can walk in agreement with Jesus Christ and fellowship with Him every day. Would you like that? So would He. He's waiting for you.
Next time: New Year's what?
Christina Ferris of Somerset is part of Evangelical Christian Church Ministries, an organization committed to spreading the Gospel through the teaching and preaching of the Word of God. ECCM is an impartial group, caring only for the saving and nurturing of souls in Christ Jesus. She can be reached at: revcmf@comcast.net.


text:
College Gridiron 365
Big 12 receivers to watch in 2015
By Matt Murschel
Look around the Big 12 and you'll find a bevy of talented receivers. Here is a look at a handful of those players who return for the 2015 season:
WELCOME BACK …
Corey Coleman, Baylor: Baylor has a rich history of producing wide receivers capable of putting up big numbers in a season. The Bears had two of them last season including Coleman, who joins receivers like Antwan Goodley and Terrance Williams with 1,000 or more receiving yards in a season. He led the team in receptions (64), receiving yards (1,119) and receiving touchdowns (11).
Jakeem Grant, Texas Tech: Grant's been among the elite receivers in the Big 12 over the past few seasons – growing better every year. In 2014, he led Texas Tech in receptions (67), receiving yards (938) and was tied for second on the team in receiving touchdowns (7). There is no reason to expect the Red Raiders not to put up big passing numbers again this season so expect big things again for Grant.
Sterling Shepard, Oklahoma: Shepard earned a spot as a semifinalist for the Biletnikoff Award, given to the nation's best wide receiver, after leading Oklahoma in receptions (51), receiving yards (970) and receiving touchdowns (5). The addition of new offensive coordinator Lincoln Riley and the return of the Air Raid offense to Norman provides Shepard more opportunities in 2015.
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KD Cannon, Baylor: Cannon, along with Corey Coleman, provides Baylor with an outstanding 1-2 punch from the receivers. As a true freshman, he was third on the team in receptions (58) while finishing second on the team in receiving yards (1,030) and second in receiving touchdowns (8). Antwan Goodley's departure means Cannon could compete for the top spot in the group next season.
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Josh Doctson, TCU: There's no denying the fact Josh Doctson benefited greatly from the offensive system put in place by Sonny Cumbie and Doug Meacham at TCU. The talented wide receiver nearly doubled his receptions (63) from the previous season and surpassed the 1,000-yard mark in receiving yards while adding 11 receiving touchdowns in 2014.
Brandon Sheperd, Oklahoma State: Sheperd's one of a trio of talented wide receivers at Oklahoma State last season. He finished the year leading the team in receiving yards (737) and receiving touchdowns (5) and ranked third in the Big 12 with an 18.9 yards per catch average.
Matt Murschel can be reached at mmurschel@tribpub.com. Follow him on Twitter at @osmattmurschel.
Terrance Williams