text:
\section{Introduction}

\newlength{\figurerefwidth}
\setlength{\figurerefwidth}{\columnwidth}

Chemical concepts as fundamental as atomic orbitals (AOs)
in molecules, covalent bonds, or even partial charges,
do not correspond to physical observables and thus cannot be unambigously defined in pure quantum theory.
This leads to the unpleasing situation that
quantum chemistry can tell us benzene's heat of formation with
<2 kJ/mol accuracy,\cite{harding:benzene}
but, strictly speaking, neither that it has twelve
localized $\sigma$-bonds and a delocalized $\pi$-system, nor what the partial
charges on the carbons are.
Chemical bonds have even
been compared to unicorns---mythical creatures of which everyone knows
how they look, despite nobody ever having seen one.\cite{frenking2007unicorns}

However, qualitative concepts are of essential importance for practical chemistry,
and thus a large number of competing techniques were developed for extracting them from quantum chemical calculations.
In particular, Bader's atoms in molecules\cite{bader:aim} and Weinholds
natural atomic/bond orbital analysis (NAO/NBO)\cite{weinhold:npa,weinhold:nho} are widely
used for interpreting molecular electronic structure.
Nonetheless, the former is known to produce counter-intuitive results in
many cases,\cite{Guerra:VDD}
and the latter, while undoubtedly having brought countless successes
in chemical interpretation, is complicated and pre-imposes
various non-trivial assumptions.
In particular, NBO analysis is based
on the two notions that atomic orbitals (AOs) in molecules have spherical symmetry
and can be
obtained by a particular complex series of transformations,\cite{weinhold:npa} and
that a Lewis-like bonding pattern for any given
molecule \emph{exists} and only needs to be found---by comparing the
wave function to all possible Lewis patterns.\cite{weinhold:nlmo}
While normally applicable,
violations of both assumptions are conceivable in unusual bonding situations,
and might then lead to erratic interpretations.

We here present a new technique to connect quantitative
self-consistent field (SCF) wave functions to a qualitative chemical picture.
This technique is essentially free of empirical input, allows for \emph{computing}
the nature and shape of chemical bonds, and is not biased towards any preconceived
notion of bonding.
This is achieved by first defining a new intrinsic minimal basis (IMB),
a set of perturbed core- and valence AOs which can exactly describe the occupied molecular orbitals (MOs)
of a previously computed SCF wave function. We will show that the intrinsic AOs
(IAOs) thus defined can be directly interpreted as the \emph{chemical} AOs, and
that partial charges and bond orbitals (IBOs) derived from them
perfectly agree with both experimental data and intuitive chemical concepts.
In particular, we find a natural \emph{emergence} of the Lewis structure of molecules.

While other IMB constructions have been developed before,
\cite{Mayer:TheEffectiveMinimalBasis,lee:PolarizedAtomicOrbitals1,HeadGordon:PolarizedAtomicOrbitals2,auer:EnvelopingLocalizedOrbitals,Ruedenberg:MoleculeIntrinsicMinimalBasis,subotnik:LocalizedVirtuals,ruedenberg:ExactRepresentationOfRdm,laikov:IntrinsicBasis}
most are rather complex and so far none has found widespread use comparable to Bader or NAO analysis.
Our contribution is a IMB which is
simple and efficient,
its use in constructing bond orbitals,
and the demonstration that this combination shows excellent promise for
interpreting chemical bonding and reactivity.
The technique thereby provides a firm quantum mechanical
basis for ubiquitous fundamental concepts.

\section{Construction of intrinsic orbitals}
Assume that we have computed a molecular SCF wave function $\ket{\Phi}$.
$\ket{\Phi}$ is defined by its occupied MOs $\ket{i}=\sum_\mu \ket{\mu}C^\mu_i$,
where $\mu\in B_1$ are basis functions from a large basis set
$B_1$. The key problem in interpreting wave functions is that
the basis functions $\ket{\mu}$ cannot be clearly
associated with any atom; each function will
contribute most where it is most needed, and due to $B_1$'s
high variational freedom, this often is not on the atom it is placed on.
On the other hand, if one were to expand the MOs over a
minimal basis $B_2$ of free-atom AOs (i.e., a basis of accurate AOs, but e.g., with only AOs
1s,2s,2px-2pz for each C atom), the wave function would be easy to
interpret.
But it would be inaccurate, and might be even qualitatively incorrect, because
free-atom AOs contain no polarization due to the molecular environment.
We thus propose to first calculate an accurate wave function $\ket{\Phi}$,
and then to form a set of polarized AOs $\ket{\rho}\notin B_2$
which can exactly express $\ket{\Phi}$s occupied MOs $\ket{i}$.
For this, we first split the free-atom AOs $\ket{\tilde \rho}\in B_2$
into contributions corresponding to a depolarized occupied
space $\tilde O = \sum_{\tilde i}\ket{\tilde i}\bra{\tilde i}$ and
its complement $1-\tilde O$. The depolarized MOs are obtained as
\begin{align}
   \{\ket{\tilde i}\} &= \operatorname{orth}\{P_{12}P_{21}\ket{i}\}
\end{align}
by projecting the accurate MOs $\ket{i}$
from the main basis $B_1$ onto the minimal basis $B_2$ (which cannot
express polarization) and back.\footnote{A projector to space $Y$ maps any point $x$ to its closest point $y\in\mathrm{span}(Y)$, i.e. $P x = \mathrm{argmin}_{y\in Y}\Vert x - y\Vert_2$]}
We can then get the
polarized AOs $\ket{\rho}$ from the free-atom AOs $\ket{\tilde \rho}$
by simply projecting their contributions in $\tilde O$ and $1-\tilde O$ onto their polarized counterparts
$O=\sum_i \ket{i}\bra{i}$ and $1-O$:
\begin{align}
   \ket{\rho} &= \Bigl(O \tilde O + (1-O)(1-\tilde O)\Bigr)P_{12}\ket{\tilde \rho}.\label{eq:ib}
\end{align}

Thus, to construct the polarized AOs it is sufficient
to load a free-atom basis, calculate its overlap with the main basis
and within itself, and perform the numerically trivial projection \eqref{eq:ib}.
Contrary to the related approach of Ref. \onlinecite{Ruedenberg:MoleculeIntrinsicMinimalBasis},
no functional optimization or reference to virtual orbitals is required.
In this article we will also symmetrically orthogonalize the vectors obtained
by \eqref{eq:ib}, to arrive at an orthonormal minimal basis which divides
the one-particle space into atomic contributions;
the latter will be referred to as
intrinsic atomic orbitals (IAOs).

While the construction makes reference to free-atom AOs
through basis $B_2$, it must be stressed that these are
\emph{not} empirical quantities. Free-atom orbitals can be \emph{calculated} with any high-level
quantum chemistry program.
However, in practice this is not even required
because they are already tabulated as part of several standard basis sets;
here we take the AO functions of cc-pVTZ.\cite{bib:SupplMath}

Since IAOs are directly associated with atoms, they can be used
to define atomic properties like partial charges.
Let us denote the closed-shell SCF density matrix as
$\gamma=2\sum_i \ket{i}\bra{i}$, where $i$ are the occupied MOs.
We can then define
\begin{align}\label{eq:PartialCharge}
   q_A = Z_A - \sum\nolimits_{\rho\in A} \braket{\rho|\gamma|\rho}
\end{align}
as the partial charge on atom $A$, where $Z_A$ is the atom's nuclear charge and
$\rho$ its IAOs.
\tabref{tab:BasisSetDependence} shows that the
partial charges obtained are insensitive to the basis set,
follow trends in electronegativities, and some
defects seen in other methods (e.g., Bader's description of the CN
bond in HCN as ionic) are absent.
Partial charges will be further analyzed below.

\begin{table}
   \begin{tabular}{llcclccc}
   \hline\hline
                     &{\rule{3ex}{0ex}}& \multicolumn{2}{c}{CH$_4$} &{\rule{4ex}{0ex}}& \multicolumn{3}{c}{HCN}
   \\\cline{3-4}\cline{6-8}
        Method/Basis && C & H && H & C & N
   \\\hline
           IAO/def2-SVP$^a$          &  & --0.49 &  +0.12 &    &  +0.21 & --0.01 & --0.20
   \\      IAO/def2-TZVPP$^a$        &  & --0.52 &  +0.13 &    &  +0.22 & --0.01 & --0.21
   \\      IAO/def2-QZVPP$^a$        &  & --0.52 &  +0.13 &    &  +0.22 & --0.01 & --0.21
   \\      IAO/cc-pVTZ$^a$           &  & --0.52 &  +0.13 &    &  +0.22 & --0.01 & --0.21
   \\      IAO/aug-cc-pVTZ$^a$       &  & --0.52 &  +0.13 &    &  +0.22 & --0.01 & --0.21
   \\[1ex] Bader/TZ2P$^b$           &  &  +0.05 & --0.01 &    &  +0.19 &  +0.82 & --1.01
   \\[1ex] Mulliken/DZ$^b$          &  & --0.98 &  +0.25 &    &  +0.34 &  +0.03 & --0.38
   \\      Mulliken/DZP$^b$         &  &  +0.05 & --0.01 &    &  +0.16 &  +0.28 & --0.44
   \\      Mulliken/TZ2P$^b$        &  &  +0.61 & --0.15 &    & --0.02 &  +0.27 & --0.25
   \\\hline\hline
   \end{tabular}
   \caption{(a) Hartree-Fock partial charges
      via \eqeqref{eq:PartialCharge}.
      (b) Kohn-Sham/BP86 partial charges\cite{Guerra:VDD} via
         the Bader and Mulliken methods.
   }
   \label{tab:BasisSetDependence}
\end{table}

IAOs provide access to atomic properties, but
it is often desirable to get a clearer picture of
molecular bonding. We now show that by combining the
IAOs with orbital localization in the spirit of Pipek-Mezey (PM),\cite{pipek:PMlocalization}
one can explicitly construct bond orbitals (IBOs), without any empirical
input, and \emph{entirely within the framework of MO theory}.
A Slater determinant $\ket{\Phi}$ is invariant to unitary
rotations $\ket{i'} = \sum_i \ket{i} U_{ii'}$ amongst its occupied MOs $\ket{i}$.
We can thus define the IBOs by maximizing
\begin{align}\label{eq:LocFunctional}
   L = \sum_{A}^\mathrm{atoms}\sum_{i'}^\mathrm{occ} [n_A(i')]^4
\end{align}
with respect to $U_{ii'}$.
Here $n_A(i') = 2\sum_{\rho\in A}\braket{\rho|i'}\braket{i'|\rho}$ is the number of $\ket{i'}$'s electrons
located on the IAOs $\rho$ of atom $A$.
This construction effectively minimizes the number of atoms an orbital
is centered on.
The exponent 4 is preferred over the exponent 2 of PM because it leads to discrete
localizations in aromatic systems; for other systems both exponents lead to effectively identical results.

\begin{figure}
   \centering
   \includegraphics[width=.95\figurerefwidth]{acrylic_acid-orbtials.pdf}
   \caption{IBOs of acrylic acid: {\bf a} and {\bf b}:
      two $sp$-hybrid and two $p$ lone pairs (1-center orbtials).
      {\bf c} and {\bf d}: eight $\sigma$-bonds and two $\pi$-bonds (2-center orbitals). Core orbitals are not shown.
      }
   \label{fig:AcrylicAcidILO}
\end{figure}

\figref{fig:AcrylicAcidILO} shows IBOs computed for
the acrylic acid molecule.
Here 16 of 19 occupied MOs can be expressed to >$99\%$ by charge
with IAOs on one or two centers, respectively. The three other
MOs are part of a $\pi$-system:
The oxygen $p$ lone pairs (which have about 7\% bonding character),
and the C$=$C $\pi$-bond (which has about 3\% contributions
on the third C atom, and about 1\% on the doubly-bonded O).
In total, we see a direct correspondence of the obtained
IBOs with the classical bonding picture: $\sigma$-bonds, $\pi$-bonds,
and lone pairs are exactly where
expected, and the $\pi$-system is slightly delocalized.
We stress again that these 19 IBOs
are \emph{exactly equivalent} to the occupied MOs
they are generated from: Their anti-symmetrized product is the SCF
wave function, and this is a valid representation of its
electronic structure.
Note that the IBO construction
makes no reference to the molecule's Lewis structure whatsoever;
the classical bonding picture thus arises as an emergent
phenomenon rooted in the molecular electronic structure itself, even if not imposed.

The major improvement of IBOs over PM orbitals is that they are based on IAO
charges instead of the erratic Mulliken charges (cf. CH$_4$ in \tabref{tab:BasisSetDependence}).
As a result, IBOs are always well-defined, while PM orbitals are
unsuitable for interpretation because they are
unphysically tied to the basis set (they
do not even \emph{have} a basis set limit).
IBOs lift this weakness while retaining and even improving on PM's computational
attractiveness.\cite{bib:SupplMath}

\section{Consistency with empirical facts}
Our hypothesis is that IAOs offer a chemically sound
definition of atoms in a molecule.
But since these are not physically observable,
this claim can only be backed by consistency with empirical laws and facts.\cite{Meister:PrincipalComponentsOfIonicity}
We thus now investigate
whether partial charges derived
from IAOs follow expected trends based on electronegativies,
C 1s core level shifts, and linear free-energy relationships
for resonance substituent effects (Taft's $\sigma_R$).
We then go on to see how IBOs reflect bonding in some non-trivial molecules.

We saw in \tabref{tab:BasisSetDependence} that, unlike Mulliken charges,
IAO charges are insensitive to the employed basis set,
and unlike Bader charges,
IAO do not erronously describe the CN bond in HCN as ionic.
We now follow Ref.\ \onlinecite{Guerra:VDD} and investigate
IAO charges in relation
to electronegativity $\chi$ diffences.
We start with the series CH$_3$X (X=F, Cl, Br, H). Due to the
(Allen\cite{Allen:Electronegativities}) electronegativities
(F: 4.193, Cl: 2.869, Br: 2.685, C: 2.544, H: 2.300),
we expect halogens to have a negative charge, getting smaller in the series,
and hydrogen to have a positive charge.
As shown in \figref{fig:HalogenMethanes}{\bf a},
this is what we find.
In \figref{fig:HalogenMethanes}{\bf b}, we show the series YH$_4$ (Y=C, Si, Ge). We find
charges in close correspondence with $\chi$ (C: 2.544, Si: 1.916, Ge: 1.994),
and the inversion that $\chi(\mathrm{Si})<\chi(\mathrm{Ge})$ is properly reflected.
If we extrapolate the curves in {\bf a} and {\bf b} to $\Delta\chi=0$,
we find in both cases that $q(X)\approx 0$ and $q(Y)\approx 0$, respectively.
That is, if there is no difference in electronegativity, IAO partial charges predict
no bond polarization. This consistency with empirical electronegativies is further
reflected in the almost linear shapes of the curves.
In the series CH$_{4-n}$F$_n$ (n=0$\ldots$4),
we find C partial charges of -0.52, -0.01, 0.44, 0.85, 1.23. The charge increase by $\approx$0.5e$^-$ per fluorine atom
agrees with the understanding of CF bonds in organic chemistry\cite{ohagan:CFbond}
and earlier calculations,\cite{wiberg:cf4}
contrary to the much smaller charges found in Hirshfeld and Voronoi deformation density (VDD) analysis.\cite{Guerra:VDD}

\begin{figure}
   \includegraphics[width=.48\figurerefwidth]{CH3X.pdf}
   \hspace*{0.02\figurerefwidth}
   \includegraphics[width=.48\figurerefwidth]{YH4.pdf}
   \caption{(a): IAO partial charges in CH$_3$X (X=F, Cl, Br, H)
      plotted against $\chi(C)-\chi(X)$. $\Delta \chi=0$ is marked by a dotted line.
      (b): Partial charges in YH$_4$ (Y=C, Si, Ge), the x-axis is $\chi(H)-\chi(Y)$.}
   \label{fig:HalogenMethanes}
\end{figure}

A different test of IAO charges can be performed by comparing to experimental data which are known to be
highly correlated with charge states of specific atoms $A$. A prime
example for this is the C 1s core-level ionization energy shift due
to the molecular environment.
This shift can be estimated\cite{siegbahn:SimplePotentialModel} as
\begin{align}
   \Delta \mathrm{IP}_\mathrm{C\,1s} = k\cdot q_A + \sum_{B\neq A}\frac{q_B}{\norm{\vec R_A-\vec R_B}} + \Delta E_\mathrm{relax},\label{eq:SimplePotentialModel}
\end{align}
where the second term is an estimate for the electrostatic potential of the
other atoms $B$, the last term is a contribution due to core orbital
relaxation, and $k$ is a (hybridization dependent) proportionality constant.
This model has been employed to calibrate
widely used electronegativity equilibration models,\cite{gasteiger:iterativeequalization}
and has been found to be perfectly correlated with both experimental\cite{guadagnini:CoreEnergiesIrAndCharges}
and theoretical\cite{deOliveira:SimplePotentialModelVsAtomicCharges} mean dipole
derivatives (which for the molecules studied here can be interpreted as charges,\cite{deOliveira:SimplePotentialModelVsAtomicCharges}
but not generally\cite{milani:IrCharges}).
\begin{figure}
   \includegraphics[scale=1.0]{C1s.pdf}
   \caption{Partial charge on sp$^3$ carbon versus experimental C\,1s
      ionization energy shift corrected for core relaxation effects
      and electrostatic potentials of the other cores (\eqeqref{eq:SimplePotentialModel}), relative
      to methane.}
   \label{fig:C1s}
\end{figure}
In \figref{fig:C1s} we show the results obtained with IAO partial charges
based on Hartree-Fock wave functions for all the sp$^3$ hybridized
molecules as studied in Ref. \onlinecite{guadagnini:CoreEnergiesIrAndCharges}.
IAO charges where used both for the abscissa and $V$, the second term in \eqeqref{eq:SimplePotentialModel}.
$\Delta E_\mathrm{relax}$ was calculated at Hartree-Fock level by a $\Delta$SCF procedure.
We here obtain a linear regression coefficient of $r=0.997$, or $r=0.9995$ if the two
outliers CF$_3$CF$_3$ and CH$_3$C$\equiv$CH$_3$ are excluded. This is the same
level of correlation as obtained with dipole moment derivatives,\cite{guadagnini:CoreEnergiesIrAndCharges}
and much higher than for CHELPS, Bader, or Mulliken charges.\cite{deOliveira:SimplePotentialModelVsAtomicCharges}

One advantage of Hilbert-space based partial charges over
real-space partial charges is that they can be split not only
into atomic contributions, but also orbital contributions.
Recently Ozimi\'{n}ski and Dobrowolski\cite{oziminski:EDA} used this freedom
to introduce a set of descriptors for the electronic $\sigma$- and $\pi$-substituent
effects, called sEDA and pEDA, and showed that they are both
internally consistent and highly correlated with empirical
substituent effect parameters like Taft's $\sigma_R$. Concretely,
for a substituted benzene R-C$_6$H$_5$, the pEDA parameter is defined as
the number of $p_z$ electrons on the six carbon atoms of the benzene ring,
relative to the unsubstituted benzene:
\begin{align}
   \mathrm{pEDA} = \sum_{i=1}^6 q_\mathrm{C_i 2 p_z}(\text{C$_6$H$_6$}) - \sum_{i=1}^6 q_\mathrm{C_i 2 p_z}(\text{R-C$_6$H$_5$}),
\end{align}
where Ozimi\'{n}ski defined this quantity based on NAO population
analysis\cite{weinhold:npa} with a specified type of wave function and basis set.
In order to demonstrate the potential of IAO charges in the interpretation of
chemical reactivity, in \figref{fig:pEDAvsSigmaR} we show that the same kind
of correlation with empirical substituent constants is also obtained when
calculating pEDA from IAO charges ($r=0.966$) instead of NAO charges ($r=0.943$\cite{oziminski:EDA}).
\begin{figure}
   \includegraphics[scale=1.0]{pEDA_vs_SigmaR.pdf}
   \caption{Correlation of pEDA based on IAO/Hartree-Fock charges
      versus $\sigma_R$ substituent constants taken from Ref. \onlinecite{hansch:SubstituentConstantsReview}.}
   \label{fig:pEDAvsSigmaR}
\end{figure}
Calculating such EDA values is computationally trivial,
which makes them an attractive quantity in the study of unusual substituents
not be contained in common tables, or for testing if the substituents
behave differently for different hosts than benzene.
Indeed, a similar idea to Ozimi\'{n}ski's has been considered previously,\cite{wiberg:SigmaPiMethane}
but was much less practical due to being based on carefully crafted real-space integration
because Hilbert space approaches were considered unreliable.\cite{wiberg:SigmaPiMethane}

A deeper insight into the nature of a molecule's bonding can be obtained
by calculating its bond orbitals.
As previously noted,
IBOs are an \emph{exact} representation of SCF wave functions,
and we have seen in \figref{fig:AcrylicAcidILO}
that they normally reflect the classical bonding concepts
one to one.
However, in many molecules the Lewis structure does not tell the entire
story. Therefore we now probe how IBOs reflect bonding in some well
known, but in different senses non-trivial molecules.
\begin{figure}
   \centering
   \includegraphics[width=.95\figurerefwidth]{benzene-orbitals.pdf}
   \caption{IBOs of benzene: {\bf a} six CC $\sigma$-bonds,
      and {\bf b} six CH $\sigma$-bonds, both localized, and {\bf c-e} one of the two
      equivalent IBO sets representing the delocalized $\pi$-system of three orbitals.
      {\bf f-h}: See text}
   \label{fig:BenzeneIBO}
\end{figure}
\begin{figure}
   \centering
   \includegraphics[width=.95\figurerefwidth]{diborane-orbtials-h.pdf}
   \caption{IBO of some molecules with non-Lewis bonding:
     {\bf a} CC banana bond and {\bf b} CH $\sigma$-bond of cyclopropane,
     {\bf c} BH $\sigma$-bond and {\bf d} BHB 2e3c bond of diborane,
     {\bf e} SO $\pi$-bond and {\bf f} SO $\sigma$-bond of sulfur trioxide.}
   \label{fig:OtherIBO}
\end{figure}

Benzene:
A straight application of the IBO construction produces the orbitals {\bf a}--{\bf e} shown in \figref{fig:BenzeneIBO}.
As expected, both the CC and the CH $\sigma$-bonds of the
system are completely localized, and can be be expressed to >99\%
with IAOs on only the two bonded centers. As a prototypical
delocalized system, this does, however, not hold for the $\pi$ system.
Two aspects are important: (i) The three $\pi$ orbitals cannot be
expressed with IAOs on less than four centers each (in {\bf c}--{\bf e} having the weights
1.000, 0.444 (ortho), and 0.111 (para)), and (ii) there are
two different maximal localizations of the functional \eqeqref{eq:LocFunctional},
orbitals {\bf c}--{\bf e} and orbitals {\bf c}--{\bf e} rotated by 60$^\circ$ in real space.
If in \eqeqref{eq:LocFunctional} we had chosen
to maximize $\sum n_A(i)^2$ instead of $\sum n_A(i)^4$,
there would even be
a continuum of maximal localizations, also including orbitals {\bf f}--{\bf h}
(which look closer to classical $\pi$-bonds), and everything
in between.
In this case the classical resonance structure
reflects the nature of the bonding well.

Cyclopropane:
According to its Lewis structure, cyclopropane is a simple alkane. However, due to
the massive ring strain one could expect that some
bonding effects are inevitable. Nevertheless, if we calculate the IBOs of this
molecule (\figref{fig:OtherIBO}, {\bf a} and {\bf b}),
we find six CH single bonds and
three CC single bonds, all perfectly localized (to >99\%)
on the two bonded centers, with no delocalization whatsoever.
However, a closer look reveals that while the carbon part of the
CH bond orbitals has about 28\% $s$ character and 72\% $p$ character,
(close to the ideal $sp^3$ hybrid values of $1/4 s + 3/4p$),
the CC bonds only have 18\% $s$ character and 82\% $p$ character.
So although they are localized single bonds,
they must be considered an intermediate between a
regular $sp^3$-hybrid $\sigma$-bond and a $\pi$-bond.
This explains the well-known similarity in reactivity
to alkenes.

Diborane: B$_2$H$_6$ has been
a serious challenge to the classical bonding picture,
with even scientists like Pauling
championing an ethane-like structure
until proven wrong irrefutably.\cite{laszlo:ADiboraneStory}
Its bridged structure was popularized in 1943,\cite{longuet:StructureOfBoronHydrides}
and spawned investigations culminating in
Lipscomb's 1976 Nobel price for his ``studies on the structure of boranes illuminating problems of chemical bonding''.
One could think that this molecule presents a challenge to
a IBO bonding analysis.
However, IBOs are just the most local exact description of a first-principles
wave function, and their construction
does not make \emph{any} reference to \emph{any} perceived nature of the bonding.
Consequently, for IBO analysis diborane
is not different than other molecules, and it uncovers diborane's
two two-electron three-center bonds (\figref{fig:OtherIBO}{\bf d})
just as its six standard $\sigma$-bonds ({\bf c}), without any problems.

\newenvironment{tightcenter}{%
  \setlength\topsep{3pt}
  \begin{center}
}{%
  \end{center}
}
Sulfur trioxide: SO$_3$ is one of the simplest ``hypervalent'' molecules,
apparently violating the octet rule.
An IBO analysis finds two oxygen lone pairs, one $\sigma$- and one $\pi$-bond
(\figref{fig:OtherIBO}{\bf e}) per oxygen.
Formally this calls for describing the SO bonds as double bonds.
However, the $\pi$-bonds have only
a small bonding component (83\% on oxygen, 15\% on sulfur),
so it is a matter of taste whether they should be called true $\pi$-bonds or not.
But in any case, they are highly localized (98\% on two centers) and
clearly not resonating, so the resonance structure
\begin{tightcenter}
   \includegraphics[width=2.5in]{so3-resonance1-bw-eps-converted-to.pdf}
\end{tightcenter}
---commonly found in textbooks---is at best misleading.\footnote{
Three double bonds are allowed here because they are polarized, and thus contribute less
than one electron per bond to sulfur's valence orbitals. Consequently,
two electrons per valence orbital are never exceeded (the quantum mechanical core of the octet rule) and neither
delocalization nor $d$-orbital participation need to be invoked.}

Bifluoride anion:
We see a similar discrepancy to textbook knowledge
in the description of FHF$^-$.
This molecule is alternatively cited as the strongest known hydrogen bond,\cite{gilli:UnifiedHydrogenBondTheory} or as an example
for a 3-center 4-electron bond (since an influential paper by Pimentel\cite{pimentel:fhfAnion}).
However, IBO anaylsis reveals that it can be perfectly described by
six F lone pairs and two HF single bonds, all completely localized.
Since the bonds are highly polarized, there is again no violation of the
octet rule: In fact, the H orbital has a population of only 0.6 electrons
total (out of the up to two electrons it theoretically could harbor), and
the nature of bonding in this molecule is not very different than in HF.

\section{Conclusions and Outlook}
The proposed IAOs offers
a simple and transparent way to relate chemical intuition to
quantum chemistry. In particular, the fact that
most simple bonds can be expressed to >99\% with IAOs on only two atoms strongly
indicates that IAOs can be interpreted as \emph{chemical}
valence orbitals in molecules. That properties of individual such orbitals can
then be directly calculated, as shown in \figref{fig:pEDAvsSigmaR},
may turn out to
be a decisive factor in future research on chemical reactivity.
Similarly, IAOs may greatly simplify the construction
of realistic tight-binding model Hamiltonians
and their use in eludicating complex correlated electronic structure phenomena.\cite{knizia:HubbardDmet,knizia:HydrogenDmet}

The proposed IBOs can help to uncover the nature
of bonding in molecules---due to their unbiased nature also in unusual cases.
However, the IBO construction's simplicity,
ease of implementation, and high runtime efficiency make it
an excellent choice also where localized orbitals are used
for purely technical reasons (e.g., in local electron correlation methods).

We acknowledge funding through ERC Advanced Grant 320723 (ASES).

redpajama_set_name: RedPajamaArXiv


text:
Who is Morgan Cryer? Bio, Wiki, Age, Career, Net Worth, Instagram, YouTube, Boyfriend Bio, Net Worth, Age, Height, Salary, Wiki
April 2, 2022 Soumen Celebrity 0
Browse to know more about Morgan Cryer's Age, Bio, wiki, Net Worth, Income, career, Education, and Family. Also know details about Morgan Cryer's Parents, Childhood, Relationship, body measurements, Images, and many more.
Morgan Cryer is an American actress and social media personality who has appeared in films, television, commercials, and also in several music videos.
Similarly, she is also popularly known for featuring in the music videos for MattyB's "Guaranteed" and "The Good Life."
What is Morgan Cryer famous for?
An American actress and social media personality.
Known for featuring in the music videos for MattyB's "Guaranteed" and "The Good Life."
How old is Morgan Cryer? Bio, Nationality, Parents
Morgan Cryer was born on 13 June 2002 in the United States. As of 2020, she is 18 years old. She is American by her nationality but her ethnicity is unknown. Similarly, her birth sign is Gemini.
Talking about her family, her mother's name is Michelle Daniels Cryer but there is no information about her father. Similarly, as per her siblings, she has an elder brother named Kyle Cryer who is also an actor.
Caption: Morgan Cryer ( Source: Pinterest)
Read Who is Lexi Rivera? Bio, Age, Career, Height, Net worth, Parents,Sibling, YouTuber, Social Media InfluencerInstagram
Talking about her educational background, the information regarding her educational background is under review. She has not shared any information about her education history to the public.
All About her Career
Talking about her career, she gave start to her career as an actress. She began doing modeling and acting since age 3. She made her debut by appearing in episodes of the TV shows The BureauandAmerican Occult.
Moreover, she also penned the short film screenplay titled The Harvest. Further, she also worked as an actress and producer for The Wages of Sin released in 2016, Company Town released in 2013, and Insurgent released in 2015.
In addition, she also made her appearance in J. Cole's music video Crooked Smile. She has also collaborated with a young American pop singer, Jacob Sartorius.
Apart from this, She also has a self-titled YouTube channel that she created on October 5th, 2012. She has posted around 8 videos on her channel. On February 13, 2017, she posted her first video titled 'Morgan Cryer Q&A #1'. The video has more than 16k views.
Similarly, her most popular video is titled 'BLACKBOUGH Swim Bikini Try on Haul #2' which has more than 104.3k views. Likewise, her other videos such as BLACKBOUGH Swim Bikini Try on Haul, Charmo Swim bathing suit haul, PLAYA DEL CARMEN 2018, Malibu Daze, Vlog #1, Vlog 2: A day in the life in LA, Vlog 2: A day in the life in LA, also has thousands of views. She has more than 3.41k subscribers on her channel.
Net Worth and Salary
Talking about her income, as an actress, and a social media personality, she has earned a good amount of money for her living. Her estimated net worth is around $100K.
Similarly, according to the social blade, she earns $20 – $320 monthly and $240 – $3.8K yearly from her YouTube channel.
Also read Who is James Charles? Bio, Age, Height, Net worth, Parents, Internet personality, Awards, CoverGirl, Gay, Instagram
Controversy and Rumors
Till now, she has not faced any kind of controversy. Similarly, there are no extreme stories about her rumors relating to her private and professional life.
Furthermore, she has maintained a clean image. She is currently focusing on her career rather than dealing with scandals.
Is Morgan Cryer single? Boyfriend, Relationship
Currently, Morgan Cryer is in a romantic relationship with Tristan Waite. However, there is no information when they began dating. The duo often shares adorable photos featuring each other in their respective Instagram handles.
Caption: Morgan Cryer With her boyfriend ( Source: Pinterest)
The couple shares a strong bond. There are no records of their separation and break up.
How tall is Morgan Cryer? Weight, Hair
She stands at a height of 5 feet 6 inches and her weight is around 50 kgs. Similarly, she has beautiful blue eyes with blonde hair color.
She has maintained a good body-shaped of 32-23-33 inches for her breast, waist, and hip size respectively.
Social Media Appearance
She is active on social sites such as Twitter, Facebook, and Instagram. She has more than 2.3k followers on Instagram and over 1.8k on Twitter.
Similarly, she holds around 2.4k followers on her Facebook account.
She also appeared in J. Cole's music video titled Crooked Smile.
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Who is Daniel Dae Kim? Wife? Bio, Wiki, Age, Career, Net Worth, Instagram, Movies, Height Bio, Net Worth, Age, Height, Salary, Wiki

redpajama_set_name: RedPajamaCommonCrawl


Venice is rated 4.5 out of 5 by 43.
This handsome full-grain leather dress shoe is so chic and sophisticated, no one will know it's a slip-resistant safety shoe. The Venice offers a leather-lined interior, removable leather-lined insole, water-resistant upper, and effective slip-resistant traction. Molto bene.
Tailored Fit: Slim-fitting design ideal for narrow feet.
Rated 3 out of 5 by Anonymous from These are nice looking shoes, but am returning them to get a another newer pair of style 1202, Statesman. These are a longer, narrower looking and fitting shoe. I usually wear 11-12 medium. I got these in 10.5, medium (I fit in 10.5 in Statesman also), which is the only width available. They were uncomfortably tight in width and the shoe extended almost 2" beyond my big toe. If they came in wide width, then perhaps they would fit, but in the medium, they just don't hack it. Also they just look like long, skinny shoes. I don't particularly care for that look.
Rated 3 out of 5 by John M. from I usually choose a wide width when offered. In the past when a wide width is not available(as with this shoe)I can easily fit into a shoe by choosing a 1/2 size larger. So even with this strategy, unfortunately, this shoe felt way to tight from the beginning even with a half size larger. This review is being written after a couple of weeks of use. I had high hope for this shoe company because I walk on slick tile surfaces that get wet from snow and ice. Even though they were very tight in the beginning my hope was the company just used a leather that would easily stretch and give a more comfortable feel. After 3 days my feet were killing me. I used a shoe tree to stretch the width a bit and now they are acceptable to wear but are not my go to shoes as I had hoped. PS Love the sole and the confidence to walk on slippery surfaces. Would be my number one shoe company if they fit right.
Rated 5 out of 5 by Bobby J. from Second time buying the exact same pair. The last pair lasted me 2 years and could've lasted longer. I just wanted a fresh pair. I did recommend these to a coworker and he bought the same shoes. Everytime we see each other I always say, "Hey man those are some nice shoes!" And hes like "Thanks man you too!"
Rated 5 out of 5 by Anonymous from The only negative is the shoe runs one size larger. Fortunately enough the exchange process is quick and simple. When I received my replacement pair they were perfect. The shoes are extremely comfortable and stylish. By far exceeded my expectations and I'm probably going to buy a few more pair soon.
Rated 2 out of 5 by Anonymous from Poor comfort Shoes were not comfortable they would not hold a shine. The inserts were thin and cheep and offeeed little if any cushion. For a shoe made for a food service professional with long days on my feet this's shoe only offers one gods thing the slip resistant sole.
Rated 5 out of 5 by JONATHAN L. from I am happy to see more variety in the men's dress shoe selection. I enjoy the look, comfort and feel of these shoes. Purchased both black/brown colors and just placed a second order to have a backup pairs in case they are discontinued down the road.


Are the elements stopping you from becoming a tenting tyrant?
Tent wherever and whenever with Napier's Truck Tent. — Photo courtesy Napier Outdoors.
Is sleeping on the ground what's holding you back from becoming a fully fledged tenting enthusiast?
The Napier Sportz Truck Tent can bridge that gap. This two-person tent fits into the bed of your truck, letting you experience the fun of tenting without the feeling of sleeping on the cold, hard ground.
Napier describes its product as "the perfect campsite wherever you park." Why waste time looking for a clean, dry, level site, when one already exists in the back of your vehicle?
Never again will you wake up with your teeth chattering from the cold, your air mattress deflated after being popped by sharp rocks and your shoes floating away in the puddles of water covering your tent floor.
The Sportz tent boasts a full rainfly, built-in storm flaps, a 4x4 awning, and rear access panels that allow you to access your truck's interior. These features allow you to be ready for whatever Mother Nature may throw at you.
Napier's Truck Tent will never let you down. Camp wherever your truck takes you. — Photo courtesy Napier Outdoors.
Three large windows and two ceiling vents allow for optimum ventilation—perfect for when your camping partner decides to take off those smelly hiking boots after a five-hour hike in the hot sun.
Napier is the only company that offers truck tents with full floor coverage. You won't have to worry about cleaning the wood chips and dirt out of your box. The Sportz model has a spacious interior and a head clearance of 5.7 feet.
This particular model works with the Sportz Link Tent, which attaches to the truck tent's door area, and creates additional space for up to four campers, and twice the fun.
The truck tent offers unlimited "campsite" options. Sleep right beside your favourite fishing spot, at the head of your next hiking trail, at your latest music festival or at your favourite provincial park.
Napier also offers models for SUV and minivan owners. For more information on truck tents and available models, visit Napier's website.
The world is your campsite with the Napier Truck Tent. — Photo courtesy Napier Outdoors.
This stackable organizer allows you to bring snacks, medicine, vitamins and other essentials wherever you need to go.
No compromises need to be made with the Lorna Jane Teddy Lined Hooded Puffa Vest. This vest's design keeps the wearer warm without the bulk, and is the perfect wind-resistant layer for every RVer.


This must be the week to debut gaming controllers for iPhones(s aapl) and iPod touch devices. Yesterday, Moga announced pre-orders for its Mogo Ace Power device and on Wednesday, Logitech counter-punched by launching its PowerShell Controller + Battery. Logitech's(s logi) accessory for iPhone 5, 5s and fifth-generation iPod touch is now available online for $99 at Best Buy and the Apple Online Store.
As the name implies, the PowerShell Controller + Battery includes an internal battery to keep your iOS 7 running after a long gaming session. The battery capacity is 1500 mAh and roughly doubles the run-time of your mobile device. To use the controller and charge your handheld, you simply insert it into the Logitech PowerShell Controller + Battery as you would any case.
Gaming controls adorn the left and right side of your iPhone or iPod touch: There's a D-pad, shoulder triggers and action buttons for gaming. Since the controller doesn't fold up — the competing Moga unit does — this won't fit in a pocket. But on the other hand, it does recharge your iPhone or iPod touch, which to me makes it a better value for the same price. On the flipside, however, there are no analog sticks which could be a big let-down to serious gamers.
I'll look to get my hands on one of these in the coming days and report back on the controls and game experience.


text:
QJ51A Tetracyclines for intramammary use

QJ51AA Tetracyclines
QJ51AA03 Chlortetracycline
QJ51AA06 Oxytetracycline
QJ51AA07 Tetracycline
QJ51AA53 Chlortetracycline, combinations

QJ51B Amphenicols for intramammary use

QJ51BA Amphenicols
QJ51BA01 Chloramphenicol
QJ51BA02 Thiamphenicol
QJ51BA90 Florfenicol

QJ51C Beta-lactam antibacterials, penicillins, for intramammary use

QJ51CA Penicillins with extended spectrum
QJ51CA01 Ampicillin
QJ51CA51 Ampicillin, combinations

QJ51CE Beta-lactamase sensitive penicillins
QJ51CE01 Benzylpenicillin
QJ51CE09 Procaine penicillin
QJ51CE59 Procaine penicillin, combinations
QJ51CE90 Phenetamate

QJ51CF Beta-lactamase resistant penicillins
QJ51CF01 Dicloxacillin
QJ51CF02 Cloxacillin
QJ51CF03 Meticillin
QJ51CF04 Oxacillin
QJ51CF05 Flucloxacillin

QJ51CR Combinations of pencillins and/or beta-lactamase inhibitors
QJ51CR01 Ampicillin and enzyme inhibitor
QJ51CR02 Amoxicillin and enzyme inhibitor
QJ51CR50 Combinations of penicillins

QJ51D Other beta-lactam antibacterials for intramammary use

QJ51DB First-generation cephalosporins
QJ51DB01 Cefalexin
QJ51DB04 Cefazolin
QJ51DB08 Cefapirin
QJ51DB10 Cefacetrile
QJ51DB90 Cefalonium

QJ51DC Second-generation cephalosporins
QJ51DC02 Cefuroxime

QJ51DD Third-generation cephalosporins
QJ51DD12 Cefoperazone
QJ51DD90 Ceftiofur

QJ51DE Fourth-generation cephalosporins
QJ51DE90 Cefquinome

QJ51E sulfonamides and trimethoprim for intramammary use

QJ51EA Trimethoprim and derivatives
QJ51EA01 Trimethoprim

QJ51F Macrolides and lincosamides for intramammary use

QJ51FA Macrolides
QJ51FA01 Erythromycin
QJ51FA02 Spiramycin
QJ51FA90 Tylosin

QJ51FF Lincosamides
QJ51FF90 Pirlimycin
QJ51FF02 Lincomycin

QJ51G Aminoglycoside antibacterials for intramammary use

QJ51GA Streptomycins
QJ51GA90 Dihydrostreptomycin

QJ51GB Other aminoglycosides
QJ51GB03 Gentamicin
QJ51GB90 Apramycin

QJ51R Combination of antibacterials for intramammary use

QJ51RA Tetracyclines, combinations with other antibacterials
QJ51RA01 Chlortetracycline, combinations with other antibacterials

QJ51RB Amphenicols, combinations with other antibacterials
QJ51RB01 Chloramphenicol, combinations with other antibacterials

QJ51RC Beta-lactam antibacterials, penicillins, combinations with other antibacterials
QJ51RC04 Procaine penicillin, dihydrostreptomycin, sulfadimidin
QJ51RC20 Ampicillin, combinations with other antibacterials
QJ51RC21 Pivampicillin, combinations with other antibacterials
QJ51RC22 Benzylpenicillin, combinations with other antibacterials
QJ51RC23 Procaine penicillin, combinations with other antibacterials
QJ51RC24 Benzathine benzylpenicillin, combinations with other antibacterials
QJ51RC25 Penethamate hydroiodide, combinations with other antibacterials
QJ51RC26 Cloxacillin, combinations with other antibacterials

QJ51RD Other beta-lactam antibacterials, combinations with other antibacterials
QJ51RD01 Cefalexin, combinations with other antibacterials
QJ51RD34 Cefacetrile, combinations with other antibacterials

QJ51RE Sulfonamides and trimethoprim including derivatives
QJ51RE01 Sulfadiazine and trimethoprim

QJ51RF Macrolides and lincosamides, combinations with other antibacterials
QJ51RF01 Spiramycin, combinations with other antibacterials
QJ51RF02 Erythromycin, combinations with other antibacterials
QJ51RF03 Lincomycin, combinations with other antibacterials

QJ51RG Aminoglycoside antibacterials, combinations
QJ51RG01 Neomycin, combinations with other antibacterials

QJ51RV Combinations of antibacterials and other substances
QJ51RV01 Antibacterials and corticosteroids
QJ51RV02 Antibacterials, antimycotics and corticosteroids

QJ51X Other antibacterials for intramammary use

QJ51XB Polymyxins
QJ51XB01 Colistin
QJ51XB02 Polymyxin B

QJ51XX Other antibacterials for intramammary use
QJ51XX01 Rifaximin

References

J51

redpajama_set_name: RedPajamaWikipedia


Learn Reiki and Live an Adventure!
The view to the left!
As the breeze from the shore kissed my skin, I felt at peace. While doing yoga on the beach before sunrise, I reflected on the past past couple years. There has been so much change and I welcome more change. I married my husband Nathan in May of 2015 and learned reiki I in July 2015 then Reiki II in August 2015. I am looking forward to becoming a Master/Teacher in a couple of weeks! After teaching in graduate school, my long time love of teaching was sealed. There is something very satisfying about sharing knowledge and then watching each student apply it in their own way. I originally went to college because I wanted to be professor of communication, but after spending time in academia wanted to find a different way to teach with less restrictions. Grading was my least favorite part, but fortunately when I hold my reiki classes, I won't have to grade anyone, but I will still be able to witness how people use the information gleaned from my classes! I would think the only want to "fail" in a reiki class would be if you didn't use it after you left the class. That would be life receiving a gift but not unwrapping it and then putting it in a cupboard you don't use. Be open to the healing light of reiki because it will help you unwrap the divine gifts already within you!
I am looking forward to the change of teaching classes this fall and winter. All the changes that reiki has helped kick start in my life has made life an adventure. Just as a disclaimer, the change you need at the soul level may not been the change you consciously want though. Just like my change to go vegan, I didn't really want to, but I fould that the change has been the answer to my prayers about health and living more connected to the divine. That change and other changes that have unfolded in my life have been fantastic because I am becoming my true self. I am becoming who I must be to move forward on fulfilling my soul's mission on earth. We are all called to bring loving spiritual energy into the physical plane of earth. To truly move forward freely, I have been working on unplugging from painful memories and toxic situations. Since this time last year, there has been lots of love, but there has also been a lot of forgiveness. I want to completely release the past. I often say the positive affirmation, "I release the past. They are free and I am free." Those affirmations are from Louise Hay's book, You Can Heal Your Life. When old memories replay in our minds, we are being shown something that needs to heal. Sometimes, things can even be so traumatic that we can't remember them on the conscious level. Giving yourself reiki can help you release the past.
Life is lived in the present moment. The only power the past has over you is the energy we give it in the present moment. If you don't believe me, please read "The Power of the Now: A Guide the Spiritual Enlightenment" by Eckhart Tolle. When you are plugged into the past, you do not have enough energy to manifest the life of your dreams in the present moment. When you are plugged into the past or the worries of what the future may hold, you are stealing from your power in the present moment. Giving reiki to myself and channeling distance reiki for my friends and family has really helped bring more of God's love and light into our everyday lives. Spending time being a channel for reiki has brought such peace to my life. Some of the changes have been a spot of internal struggle as my ego (the lower self) fought the changes my higher self (the part of your soul in heaven with God acting like a satellite in deep orbit helping your physical self stay on track with your soul mission) wanted to bring into my life. I know was a run on sentence but re-read it if you need to, because the definitions are important too. The ego fears its own extinction, so it may try to throw up roadblocks, but the ego only has as much power as you give it. Do not fear, but instead know you are completely supported by the divine. Pray prayers for protection and the highest healing available. This ego can be a yappy dog in some people or more like a rabid dog in other people, be gentle with yourself and as explore you inner self. Keep affirming "It is safe for me to look within. I am willing to change. I am changing. I graciously accept what serves my highest purpose. I release that which does not serve my highest purpose." Most of these affirmation came from "You Can Heal Your Life" by Louise Hay too. I have most of those affirmations memorized and I use them like a sword cutting through darkness to release thoughts that cross my mind. On of the lovely things I learned in "The Power of the Now: A Guide the Spiritual Enlightenment" by Eckhart Tolle is that I am not my mind; I am more than my mind. When you can become the observer of your mind, you can step back in stressful situations to see everything from a higher perspective. I could go on all day, but I have to get to the beach to do my yoga! The picture from today's post are the ones I have taken the past couple days on the beach. There are perks to waking up before everyone else and staying late enough to be the only person on the beach. If you have interest in learning reiki or setting up your own distance reiki session, please contact me. Also, if you liked this post, please share it with a friend so we can spread messages of love and light! Peace be with you!


text:
Cross Post Now
Home › Sports
Everything We Know About Houston Texans Owner Bob McNair's History Of Racism And Discrimination
The new comments shouldn't surprise to those familiar with one of the president's biggest supporters.
Written By Bruce C.T. Wright
@bctw
Bruce is based in New York City and mainly covers politics, culture, race and criminal justice. He previously worked at the Washington Post, the New York Times and the Boston Globe's Boston.com, where he was a part of the Pulitzer Prize-winning team that covered the Boston Marathon bombing and manhunt. Follow him @ BCTW on social media. @bctw
Follow @bctw
Memphis Fire Department Workers Fired For Not Rendering Aid To Tyre Nichols After Cops Beat Him
Memphis Police 'Shielded And Protected' White Cop In Tyre Nichols' Arrest Video, Ben Crump Says
Who Is Preston Hemphill And Why Hasn't The White Cop In Tyre Nichols Bodycam Video Been Charged?
Mapping Coronavirus: Places Where Black People Are Getting Hit Harder By COVID-19
Biden Has Older Black Voters On Lock, But What About The Younger Ones Who Supported Bernie?
The comparison os NFL players to prison inmates by the billionaire Houston Texans owner shouldn't come as any surprised to those who have been initiated to Bob McNair's special brand of racism. He left a set of new, indelible footprints along his already lengthy trail of racist, discriminative actions and rhetoric when he challenged exiled free agent quarterback Colin Kaepernick's national anthem kneeling protest with a single racially charged quote that was included in a new ESPN report published Friday.
READ MORE: Time For The NFL To Sign Colin Kaepernick
"We can't have the inmates running the prison," he said, referring to his fellow NFL team owners who are mostly unified against what they call disrespect to the American flag.
Considering that the country's prisons are lopsidedly flooded with Black people, a group that makes up about 70 percent of the players in the NFL, McNair's comment was poorly thought out at best, and racist at worst. The comment likely came in response to the fact that Kaepernick has sued the league over claims its owners colluded to keep him from being signed to a team.
If McNair's comments seemed over the top, it's because they were just the latest in a long line of his dog whistling that is laden with racist overtones.
It's been whispered in pro football circles that McNair prefers White quarterbacks to Black ones. If true, that would explain his apparent outrage over Kaepernick's protest of social justice for Black people in America and its lasting effect on the league, which is about 70 percent Black. The quarterback position has typically been occupied by White players.
McNair is one of the many NFL owners who donated at least $1 million to the presidential campaign of Donald Trump, who has devoted a considerable amount of time during his inaugural term to condemning the protest and siding with the owners.
His apparent discrimination doesn't only skew along racial lines. He doesn't like homosexuals, either, as evidenced by donating money "to the campaign to repeal a ballot initiative in Houston that protected gays and lesbians from forms of discrimination," HuffPost wrote over the summer.
Hammerin' Hank Aaron Stands With Kaepernick
NBA Reminds Players, Coaches That They Must Stand During The National Anthem
Bob McNair Colin Kaepernick Kneeling protest National Anthem protests NFL


One ward has re-opened at the Victoria Infirmary, leaving three still closed to new admissions due to diarrhoea and vomiting.
Eight patients are currently showing symptoms – a reduction of five from Saturday.
Dr Syed Ahmed, Consultant in Public Health Medicine with NHS Greater Glasgow, said: "It is routine procedure for wards not to admit new patients as a precautionary measure when three or more people display symptoms of diarrhoea and vomiting.
"The situation at the Victoria is reflective of what is happening in the community which has also seen a rise in the number of cases of diarrhoea and vomiting.
"Staff in the hospital have put the relevant measures in place to limit spread, and we are working closely with the hospital infection control team to monitor the situation."


Marquette University Law School's students have the unique opportunity to benefit from extended stays in other countries around the world where they can immerse themselves in different cultures and legal systems and learn from international faculties and classmates. Law School students can enroll in the summer study abroad program in Giessen, Germany, run in collaboration with the University of Wisconsin Law School and Justus Liebig University Law School in Giessen.
See more info on the MU Law School website.


IJMB STUDY CENTRES IN KATSINA STATE.
IJMB KATSINA: How to apply for IJMB in Kastina. See the list of accredited IJMB centres in Kastina.
Is there any IJMB centre in Kastina state? YES!
Katsina, usually referred to as Katsina State to distinguish it from the city of Katsina, is a state in North West zone of Nigeria. Its capital is Katsina.
This post is written to answer the question of Kano state IJMB study centers, schools that accept IJMB Certificate / result in Kastina, does KASU accept IJMB? , IJMB fees in Kastina, Duration of IJMB in Kastina, etc.
To answer the question of many about IJMB in Kastina state, we have decided to publish this post today while the IJMB registration is still in progress (you can Apply for IJMB Here).
To apply for IJMB in Ibadan study center follow the instruction below.
To apply for IJMB in Ibadan, Fill the IJMB Pre-enrollment form , then proceed to payment. Make your application payment of Five thousand Naira (N5,000).
Note: While filling out your IJMB form online, remember to select "Katsina" as your preferred Study location.
The amount for IJMB in Kastina state is detailed below.
CLICK HERE TO BEGIN IJMB REGISTRATION TO KATSINA CENTER.
Need help about IJMB Kastina? Call 08166616847.


text:
MWC signs BCS agreement
By The Denver Post | newsroom@denverpost.com
Despite misgivings and an ongoing challenge to the BCS structure, the Mountain West Conference reluctantly signed on to the BCS bowl agreement with ESPN. The MWC had been the only major-conference holdout.
University of Utah president Michael K. Young, chair of the MWC board of directors, announced Wednesday: "The Mountain West believes it has no choice at this time but to sign the agreements. If a conference wishes to compete at the highest levels of college football, and the only postseason system in place for that is the BCS, no one conference can afford to drop out and penalize its football programs and student-athletes."
The MWC's proposal for a modified playoff system and change in the BCS selection process was voted down by the presidential oversight committee.
The agreement with ESPN is unrelated to the MWC regular-season package with other networks like The Mtn. and Versus.
Natalie Meisler, The Denver Post
Fulton shines in IAAF championships.
Eleanor Fulton, a junior at Highlands Ranch High School who runs for the Zoom Track Club, ran a personal-best 6 minutes, 41.77 seconds in the 2,000-meter steeplechase to finish third in a qualifying heat at the IAAF World Youth Championships in Bressanone, Italy.
She advanced to Friday's final with McKinzie Schulz of Naperville, Ill., who finished fourth.
Empower Retirement, namesake of Broncos' stadium, cheers Kansas City's return to Super Bowl — and Denver fans aren't happy about it
The nation's second-largest retirement plan company drew the ire of Broncos Country on Twitter for cheering the Chiefs' victory in the AFC title game on Sunday.
The former Broncos quarterback married fiancée and Miss Universe 2017 Demi-Leigh Nel-Peters in a ceremony at La Paris Estate in Cape Town, South Africa, according to People magazine.
Conor McGregor's next opponent could be another fighter from Colorado
Conor McGregor made short work of Colorado's own Donald "Cowboy" Cerrone on Saturday. Now, he could be on the path of facing another of the Centennial State's finest fighters.
AP college basketball poll: CU Buffs slides down rankings after loss to Arizona
Baylor and Gonzaga were the only two teams in the top five that took care of business last week. That doesn't mean they didn't move around, too.


Give your body a firm foundation. Stand with your feet shoulder-width apart (about one foot or 30 centimeters) to help stabilize yourself.
Don't twist. Instead of bending your back to reach the object, bend at your knees, keep your chest pointed forward, tighten your abdominal muscles (your core) and lift with the strength of your legs.
And when you're setting the object down? Same thing.


IGNOU DIPP Exam Form – Check out and Download Latest DIPP – Diploma in Paralegal Practice Exam Form of upcoming IGNOU Examination of all Courses.
After Download above Exam Form please save it, fill correct details, write your DIPP Study center code, Enrollment Number, Exam Center for DIPP Exam (where you wish to appear in Exam), DIPP Course details, signature of DIPP Student etc.
After filled above DIPP Exam Form please submitted it to IGNOU Regional Center under which your Exam Center falls.
There are many of the conditions are applicable to all DIPP Candidates so please check out it from above link and compliance with all conditions.


Looking for Taylors homes on an acre or more? You've found your source. Whether you're looking for a modest house on one acre or a traditional neighborhood setting with multiple acres you'll find it in Taylors.


text:
module ActivationHelper
  def activate_parents(current_item)
    # Equipment Items have EMs and Categories that may need to be
    # reactivated
    if current_item.class == EquipmentItem
      # Reactivate the current item's category and/or Equipment Model if
      # deactivated
      category = Category.find(
        EquipmentModel.find(current_item.equipment_model_id).category_id
      )
      category.revive if category.deleted_at
      em = EquipmentModel.find(current_item.equipment_model_id)
      if em.deleted_at
        em.revive
        # reactivate all checkin and checkout procedures if reviving an
        # equipment model
        activate_procedures(em)
      end
    # EMs have Categories and checkin/checkout procedures that may need to be
    # reactivated
    elsif current_item.class == EquipmentModel
      # Reactivate the current item's category
      category = Category.find(current_item.category_id)
      category.revive if category.deleted_at
      # Reactivate all checkin and checkout procedures
      activate_procedures(current_item)
    end
  end

  def activate_procedures(em)
    em.checkout_procedures.each(&:revive)
    em.checkin_procedures.each(&:revive)
  end
end

redpajama_set_name: RedPajamaGithub


text:
On the 2,000th anniversary of his death, Emperor Augustus might have some words of gentle advice for Vladimir Putin
Two millennia have passed since Augustus left this planet but debate rages as to whether we should remember him as a hero or a scounderel
David WilliamsonPolitical Editor
Just as Augustus is blamed for dismantling the republic, will Vladimir Putin will Russian democracy weakened?
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SCHOLARS fascinated by one of the most compelling figures in human history will today mark the 2,000th anniversary of the death of the Roman emperor Augustus.
Two millennia after his death, there is still debate about whether he should be seen as a hero of civilisation who spread the wonders of the classical age across Europe or as a self-glorifying despot who wrecked the Roman republic.
If Vladimir Putin is enjoying a little August relaxation, he could do worse than spend a few moments pondering the legacy of this giant of history.
Augustus' life story is gripping. In the wake of the murder of his great-uncle, Julius Caesar, he grasped opportunities to win sources of income that would support troops; he formed alliances among the Roman elite and his military defeat of Antony and Cleopatra meant the way was clear to take the reins of what would become arguably the greatest empire the world has known.
Romans were weary of the threat of civil war among generals and longed for order. Meanwhile, the senators, the defenders of the republic, were not about to bow before a monarch or a dictator.
Augustus is a rare example of a leader whose military genius was matched by his political skills. He did not grab power in the style of a banana republic dictator.
Rather, through a string of incremental victories – not least the incorporation of Egypt into the empire – he amassed clout until he was the de facto ruler of the state, its true emperor.
Crucially, he gave Romans who might otherwise have fretted about the revolution in their midst cause to cheer.
He sponsored the arts, pursued social reform, constructed aqueducts, transformed the capital into a wonderwork of marble and – critically – brought peace to the city's citizens. He created a standing army, lessened the dread of barbarian invasions by pushing back the frontiers of the empire and ensured that Roman politics was not defined by incendiary power struggles among aristocrats.
It didn't hurt his authority that in some regions of the empire he was worshipped as a god, and when he passed away the senate voted him divine honours. As he breathed his last, he might have thought, "Well, that was a job well done."
The debate about his legacy has rumbled on for centuries and is continued by the Commemorating Augustus project.
Edward Gibbon described him as a "subtle tyrant" who took efforts to show a "tender respect" for a "free constitution which he had destroyed".
Scathingly, he wrote: "When he framed the artful system of the imperial authority, his moderation was inspired by his fears. He wished to deceive the people by an image of civil liberty, and the armies by an image of civil government."
Dante Alighieri, on the other hand, celebrated his legacy in exalted terms, arguing that "Christ willed to be born in the fullness of time when Augustus was Monarch."
He wrote: "[We] we shall find no perfect monarchy, nor the world everywhere at peace, save under the divine Monarch Augustus."
Dante might have admired Augustus because the fears that defined the life of this 13th century Florentine might not have been very different from those that the emperor banished from the lives of many Romans. The idea of stable Government, safe travel, an absence of invaders, a well-run bureaucracy, a decent water supply and a trustworthy military is still a utopian dream for billions of people around the world.
Gibbon, on the other hand, could see Augustus' sleights of hand and the way he stripped power from different branches of the state until he was considered a deity.
It is one thing for an empire to have such might concentrated in the hands of an individual when that person has enlightened intentions. But the next but one emperor after Augustus was Caligula, a despot still famed for his debauched madness.
Two emperors later, Rome was subjected to the fiery tyranny of Nero. The reigns of swathes of Augustus' successors ended in suicide or assassination; just as the capitals mighty buildings crumbled, so did the great institutions charged with preserving order.
Those barbarians eventually reached the gates and the ruins of the city are as striking now for their hubris as for their imperial majesty.
Augustus deserves to be remembered because he provides a cautionary tale for strongmen who have stability and wealth to a country that was once on the verge of chaos and daily face the temptation of amassing yet more power and wealth.
When Putin took the helm of Russia, the former superpower's military forces were creaking and exhausted, separatists threatened to strip the federation of territories while self-aggrandising ideologues sought power in a capital haunted by memories of recent coup attempts, the economy spluttered and Nato's empire expanded into the Baltics.
Today, Putin enjoys poll ratings that have shot higher than any firework. Under the nose of the world, he has annexed Crimea; he is the undisputed ruler of the Kremlin and the country's energy resources have brought Russia renewed wealth and granted Putin the power to coerce and reward the rulers of smaller states.
His challenge is whether he gives in to the temptations of autocracy or whether he seeks to leave Russia not an anointed successor but a system of government that will protect the freedom of the individual. If his reign is followed by turf wars between robber barons and wild nationalists his country and the world will suffer.
But if he blocks the path of a Russian Caligula or Nero he will win the respect of historians for centuries to come. If the ghost of Augustus visits Putin's dacha, he might have wise words for the premier.


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Ackman vows to end three years of underperformance
Scott Deveau, Bloomberg News
Bill Ackman, CEO of Pershing Square Capital, speaks at the Wall Street Journal Digital Conference in Laguna Beach, California, October 17, 2017 , Reuters/Mike Blake
Billionaire investor Bill Ackman pledged to end three years of underperformance at Pershing Square Holdings Ltd., calling recent returns "particularly unsatisfactory" at a time when markets globally have been buoyant.
Pershing Square Holdings's management company has been restructuring into a smaller, investment-centric organization whose future asset growth will be driven by results, Ackman wrote in a letter to investors. Shareholders of the U.K.-listed company will vote April 24 on a planned US$300 million tender offer, which could help to reduce the discount to net asset value the company trades at, it said in a separate statement.
"While the overall record is satisfactory for early investors, it has been disappointing for PSH investors who invested in recent years," Ackman said in the letter, included in the company's annual report released Monday. "2017 should have been a stronger year for Pershing Square."
In the report, Ackman confirmed he had sold out of his passive investment in Nike Inc. after the share price appreciated by more than 30 per cent. The activist investor made about US$100 million on the investment in just a few short months, a person familiar with the matter said last week.
Pershing Square's portfolio trades at a wide spread to intrinsic value, with catalysts that should contribute to value recognition, according to Ackman. The investment firm's idea generation engine is "intact and productive," he said in the letter.
Last year was a tough one for Ackman as his investment in Chipotle Mexican Grill Inc. continued to suffer setbacks. He also lost a high-profile proxy fight at Automatic Data Processing Inc., although this month he took advantage of a jump in ADP's share price to sell shares worth about US$125 million at a profit.
The bumps have continued into 2018 after he finally admitted defeat in his epic battle with Carl Icahn over his US$1 billion short position in Herbalife Ltd.
Ackman exits Nike stake with US$100M in profit: Report
Bill Ackman said to cede Herbalife fight, ending five-year saga
United Technologies shares rise on report that Ackman is building stake
Bombardier Inc. is destined to become a shell of its former self as the ailing plane-and-train maker struggles with liquidity, according to a former executive of one of Canada's largest pension funds.
Ottawa to avoid selling Trans Mountain as long as risks remain
The federal government is studying the best options for Indigenous communities to reap economic benefits from the Trans Mountain pipeline but Ottawa is not planning to sell the project while legal and political risks remain.
Alberta court approves Encana reorganization
Encana Corp. says an Alberta court has approved the oil and gas company's reorganization that will see it move its headquarters to Denver from Calgary and change its name to Ovintiv Inc.


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Awning A window that is hinged from the top so that it creates an angled awning when opened.
Casement A window operated by a hand-crank at the bottom and with hinges on the side so that it can swing outward like a door.
Bay Three or more sided windows that jut out from the home's exterior at a 30° or 45° angle.
Slider Two windowpanes set along a horizontal track that functions like a sliding patio door.
After choosing the windows that fit with your interior design, you should think about how to dress them — this is an important step because choosing the wrong décor could make your brand-new purchases look bad. For instance, bay window treatments need to account for the design's multiple panes and its awkward corners, or else the surfaces should be left completely bare. Figure out what types of window treatments you prefer for your home based on appearance, price and desired function — if you want to block out sunlight, hard treatments like blinds or shutters are effective, whereas sheer curtains are best for letting the sunshine filter inside.
There's no need to limit yourself to just one style or treatment, so feel free to explore all of the fantastic possibilities. With a little bit of effort, you can find the right windows and décor that will reflect your unique taste and personality.


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General Surgery and Urology
Protective Effects of Cannabidivarin and Cannabigerol on Cells of the Blood-Brain Barrier Under Ischemic Conditions.
(785) Cann.pdf
England, Tim
O'Sullivan, Saoirse
Blood–Brain Barrier
Cannabidivarin
Cannabigerol
Ischemia
Neuroprotection
Background and Objectives: Preclinical studies have shown cannabidiol is protective in models of ischemic stroke. Based on results from our recent systematic review, we investigated the effects of two promising neuroprotective phytocannabinoids, cannabigerol (CBG) and cannabidivarin (CBDV), on cells of the blood-brain barrier (BBB), namely human brain microvascular endothelial cells (HBMECs), pericytes, and astrocytes. Experimental Approach: Cultures were subjected to oxygen-glucose deprivation (OGD) protocol to model ischemic stroke and cell culture medium was assessed for cytokines and adhesion molecules post-OGD. Astrocyte cell lysates were also analyzed for DNA damage markers. Antagonist studies were conducted where appropriate to study receptor mechanisms. Results: In astrocytes CBG and CBDV attenuated levels of interleukin-6 (IL-6) and lactate dehydrogenase (LDH), whereas CBDV (10 nM-10 μM) also decreased vascular endothelial growth factor (VEGF) secretion. CBDV (300 nM-10 μM) attenuated levels of monocyte chemoattractant protein (MCP)-1 in HBMECs. In astrocytes, CBG decreased levels of DNA damage proteins, including p53, whereas CBDV increased levels of DNA damage markers. Antagonists for CB1, CB2, PPAR-γ, PPAR-α, 5-HT1A, and TRPV1 had no effect on CBG (3 μM) or CBDV (1 μM)-mediated decreases in LDH in astrocytes. GPR55 and GPR18 were partially implicated in the effects of CBDV, but no molecular target was identified for CBG. Conclusions: We show that CBG and CBDV were protective against OG mediated injury in three different cells that constitute the BBB, modulating different hallmarks of ischemic stroke pathophysiology. These data enhance our understanding of the protective effects of CBG and CBDV and warrant further investigation into these compounds in ischemic stroke. Future studies should identify other possible neuroprotective effects of CBG and CBDV and their corresponding mechanisms of action.
Cannabis Cannabinoid Res. 2021 Mar 17. doi: 10.1089/can.2020.0159. Online ahead of print.


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The Aloha Isle Refreshment stand has just moved. It has magically been transported to where the Sunshine Tree Terrace had been located, just behind "The Magic Carpets of Aladdin" attraction and next to the Enchanted Tiki Room.
Known for it's Dole Whip treats and fresh-cut Pineapple Spears the guest favorite receives a lot of foot traffic. There has never been much seating around Aloha Isle, and that still remains the case. However there is seating around, if you are willing to walk a bit. A least the second hand smoking area is now far, far away from our beloved Dole Whip Floats.
This general area will be receiving a bit of a makeover in the coming months, and it looks like this move may have been made so that Aloha Isle could continue to stay open, as this new location is just on the edge of the area that is being refurbished.


I'd much rather see the world through the eyes of a child. They have an innocence about them that is genuine and very real. It seems as you grow into adulthood you lose that innocence and once you do it is gone forever. Did you ever see a child's eyes light up at Christmastime as they stand in line to tell Santa what they want for Christmas? They are full of excitement and quiet anticipation as their whole world revolves around that single moment in time leading up to sitting on Santa's lap and truly believing in their heart that they were good this year as they try to remember to mention everything they hope that he will leave for them underneath the family Christmas tree. It is what is so wonderful about being a child and it brings a smile to every parent's face as they reflect on that very special time when they too were a child.
Children have no preconceived notions as they are not yet tainted by experience and they say things both honestly and sincerely as they were taught. They don't ever sugar coat what they say because they have no reason to and they have not adapted that practice yet into their young lives. They are spontaneous and are very perceptive. They are very focused in what they want and there is no question about it. I always remember when I was a child and I would say something to catch my parents attention they would always exclaim "out of the mouth of babes!" I find I say that as well when our son says something that brings a smile to my face and a realization that he makes some amazing observations as he expresses them in his own way.
If I could capture the youth, the innocence and the cuteness of a child at that precious time of their early childhood and market it I would be a rich man. The reality is that our lives are enriched by our children and when we capture them in photos or on video we are capturing something very priceless because those memories are something we need to preserve and save so when our children are grown up we will have something to have as a keepsake and a gift to show them to preserve that very special time in their lives. When we as parents see our children grow up it is a wonderful joy but we feel a bit sad as we grow older and our children out grow their youth and innocence. It is a reality we all have to face but we wish to bond with our children for as long as we can and remember those years and never let them pass us by. Childhood is a gift that we as parents get to enjoy in raising our children because memories of our childhood have long passed us by and the memories are distant and we were too young to remember it. Our children give us this truly wonderful gift of living through and experiencing childhood through their eyes and this is what makes us who we are and teaches us the whole essence of what life is all about.
On the subject of kids and the things they say I have fond memories of a TV program our family used to watch when I was a kid with the host, Art Linkletter and later Bill Cosby. I always loved the segment when they each would ask the young kids, both boys and girls questions to see their responses and the things they would say, so innocently really made you smile and laugh because it was so natural and precious. They really had a way with kids and capturing them so naturally providing the TV viewer with some really funny moments. It was light hearted and fun family entertainment. Kids say the darnedest things was the catch phrase and it was a show I always enjoyed because it captured the very innocence of childhood and the spontaneity of a child.
On the subject of kids and the things they say I have fond memories of a TV program our family used to watch when I was a kid with the host, Art Linkletter and later Bill Cosby. I always loved the segment when they each would ask the young kids, both boys and girls questions to see their responses and the things they would say, so innocently really made you smile and laugh because it was so natural and precious. They really had a way with kids and capturing them so naturally providing the TV viewer with some really funny moments. It was light hearted and fun family entertainment. Kids say the darnedest things was the catch phrase and it was a show I always enjoyed because it captured the very innocence of childhood and the spontaneity of a child..
Children touch our hearts and make us whole. We become better and more responsible when a precious baby comes into our life and our lives will forever be changed in such a beautiful way that will make every day special and something to look forward to. Children keep us alive and make us feel needed and give us what we always wanted, a family. A mommy, a daddy and a baby make a family and when we have that in our life we will realize there is nothing greater than that. The pure joy of holding your baby in your arms close to your heart will make the toughest of men a tiny bit softer when they hear the precious heartbeat and feel them lay against them as they breath and sleep in their arms completely trusting and oblivious to all around them.
As a parent you realize it is just you and the baby and all you wish for when you hold your baby close to your heart is that the moment will last forever because you will never experience a bond as beautiful then that. I get very emotional when I think back to the days when I first held my son in my arms and I remember taking a mental note of how tiny he was and how special I felt holding him realizing how totally dependent he was and how truly wonderful and beautiful he was. Life is truly incredible when you get to share it with others, especially your wife and child. Family is what we all need in our life and experiencing childhood again but now with a child of our own is the best present we could ever ask for. We learn so much from our children that we can write a book of all the experiences, precious moments and joys they provide us throughout the years. We should realize early on how important it is to document this and keep the memories alive in our hearts and our minds. There is nothing that can compare to a child's smile and the words spoken by them of "I love you, mommy and daddy!" This really makes my day and puts things into proper perspective.


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Gutiérrez to GOP and Trump Admin: 'Need Our Help? Release the 800,000 DREAMers You Hold Hostage'
By: Latino Rebels
This Thursday on the floor of the House of Representatives, the words of Illinois Rep. Luis Gutiérrez:
Here is the text of his remarks provided by his office:
Floor Remarks
Mr. Speaker, interesting meeting yesterday with General Kelly. Twenty-five Members of Congress, almost all of whom are descendants of immigrants who came here with nothing —whose parents came here with nothing— sat down with the Chief of Staff to the President of the United States and he said basically, we were the wrong kind of people in America. And that people like our parents that came here to this country really are bringing the country down. Because when he says he is for a merit based system of immigration, he's saying he's not for people like my mom and my dad being able to come to this country.
But interestingly because all of us whose families came to this country because of family-based immigration system wound up being Members of the U.S. House of Representatives.
But he was saying, you know, I'm meeting with a group of Congressmen, but you really shouldn't be here, because your parents are really tearing the country apart and bringing it down.
That is really what he means when he says he wants to replace the system we have with a merit-based system.
And that was very telling in the meeting yesterday.
But, we Democrats want a system that is family-based, that's the system that Democrats want, because we believe that businesses are started by immigrant families and it is essential for their families to be united as they come to this country so that they can achieve American success and together, all of us can achieve the American dream.
And that's exactly what they want to stop, with the merit-based system, unless of course the immigrants come from Norway, then they can continue to come.
We hear this from the party of family values and the party of Donald Trump—who even employs his children at the White House. The Trump Organization —just think about it— here's an organization where the dad created the business, handed it down to the son, and his son is going to hand it down to his children, but they don't want immigrants to do exactly the same thing and follow the same course that has been so successful for the President of the United States.
And here is something else we learned from the Chief of Staff: That when people from one party work with people from another party, that's not bipartisanship, the General said. Bipartisanship as defined by General Kelly and this White House is when people with completely different and opposite views of the world work together.
So only a Senate deal between people who believe in immigration and those who don't believe in immigration and want to end the immigration system as it is —unless you come from Norway— that's the only way it's bipartisanship.
That's like saying if a Republican and a Democrat work together on an environmental issue, it's not bipartisanship because it is a Republican and a Democrat. Unless the Democrat and the Republican are a person that believes in climate change working together with a Republican who thinks climate change is a hoax created by the Chinese.
You know what kind of legislation you get? You get nothing. You get a stalemate. You do not move the agenda forward, but that is their definition of bipartisanship. And that's what we learned at the meeting yesterday.
Look, Democrats and Republicans are working together —Senator Graham, Republican, Senator Durbin, Democrat— they put a proposal on the table and the President rejected it.
That includes, just so we are clear, Democrats giving up things that are unprecedented in that Senate deal that was put on the President's desk.
And Members of the Hispanic Caucus meeting with General Kelly cannot fathom supporting the Senate deal. But guess what, that's bipartisanship. That's what it comes down to.
Which brings us to the votes this week.
Republicans might not need our help, because you're the majority party, we're the minority party.
But just in case you do need our help in getting a budget approved, I want you to know that we are ready to stand to help keep the government open and to approve a budget. But what I learned from the meeting with General Kelly that everybody should understand is that Democrats are more united than ever before.
If you want to take the help —our help— on the budget, you've got to release the 800,000 Dreamers you are holding hostage. You've got to do it.
Democrats aren't going to blink. We're going to stand by our values.
There comes a time when if you say you stand for justice, you have to actually take a stand and hold it and not back down.
And that's what Democrats are going to do this week. We're not going to back down.
Need our help? Release the 800,000 Dreamers you hold hostage. And guess what, we are ready to pay a handsome ransom for their release.
Immigrant Activists Call for Swift Action From Biden…
VIDEO: Second Set of Legislative Hearings About…
Meet Senator Cory Booker's Latina Chief of Staff


Check out our reviews of The Fancy pants Adventures, Crazy Horses and Final Freeway 2R!
The IAP's are such a strange addition. This will sell by the bucketload, so why try and wring very penny out of players? greed.
I love Flight Control! but I hate having to pay for a game AND see additional in app purchases. Not smart.
I just get the feeling it wasn't the original Flight Control team who worked on this. The whole thing just lacks that polish and character the original had.


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The Sunday Telegraph has tipped the new-look Spicks and Specks team: Josh Earl, Adam Richard and Ella Hooper.
The three will form the next generation of Spicks and Specks when it is revived on ABC1 in 2014.
The show was due to return this year but was delayed by the broadcaster.
Comedian Josh Earl (pictured) has performed in comedy festivals, and appeared on Spicks and Specks, Talkin' 'Bout Your Generation and Adam Hills Tonight. He describes himself as an ex school librarian, ageing hipster and a cake enthusiast.
"The format will be refreshed including new games," an ABC spokesperson said.
Josh Earl – Another musical "comedian" using songs to cover up the fact he has no jokes.
Adam Richard is okay as a guest, but as a permanent cast member? His schtick is going to wear thin. Fast.
No one knew who Adam, Myf and Alan were when it began. Give them a chance!
I have to agree that the show should have a new title, given the new array of hosts.
To cite ABC popular music history, Countdown Revolution was a flop but Recovery was not.
Spicks and Specks was given a funeral. Let it stay dead. It's life could have been extended through host replacement while alive, but it was not.
What's that old saying…you can't catch lightning in a bottle. This remake is on a hiding to nothing.
Ella Hooper is a great choice I reckon and I haven't heard of the other two which is great considering what 10 do, with the same people in everything they trot out. Now just bring back GNW to the ABC where it belongs including Paul.
I wish they'd simply ditch the name and start afresh – there's definitely room for a music quiz show, but it's fighting an uphill battle by retaining the brand.
Just stop with the remakes of everything!
I would much rather continue to watch the reruns of the old series, every night. Still funny. I don't hold out much hope for a remake. Adam, Myf and Alan are hard acts to follow. I never though Adam Richard was very funny. Never heard of the new host.
Ella Hooper is a good choice. Adam richard, meh. Don't know who Josh is though.
It won't be as good as the original. Why don't they just make up a whole new game show using these three?
Earl has a very warm presence and comes across as a nice guy. You don't need much more to host that show. Adam Hills (while I like his stand-up) was never particularly funny on the show.
Adam Richard is horribly miss cast. ABC audiences will not watch high camp. You've only got to look at the ratings for Outland to realise that.
They should have done what Buzzcocks and Have I Got News For You did when they lost their host, kept it going with revolving hosts and guests until they picked people. It would have been a great novelty and given them plenty of time to test people.
I am a little disappointed they didn't choose a female comic to be a team captain or the host.
Adam Richard? Can someone explain his appeal please? I just don't get it.
Ella Hooper I agree with s she used to be a regular on the old version. Adam Richard is OK but don't know the host so I hope he is as good as Adam Hills at keeping the show together.


Over a 4-8 point hand with a 6 card minor, it is important that opener can rebid 3 of either major so that one can choose between 3NT and 4 of a major. So to use transfers effectively, we would have to include the hands with 5♠ and 4 of another suit in 2♥, which overloaded it.
Over the 4441 hands, we play 4♦ as an endbid. All other bids are slam tries, with the first bid over it as serious. As we are restricted to 4-8, we do not normally ask for keycards.
I think that they should be required to accuse the pair of something concrete, and the pair are suspended until they have been investigated and had a chance to defned themselves.
Then maybe it is fair that what they are accused of is not in the public domain if the pair themselves do not want to publish it. But at least the pair should be told the reason, and there should be a requirement for investigation and ruling in a reasonable period of time.
You should contact 2 polls, with the correct and wrong information. Then see the difference.
It depends on the agreement about what the double means. If it is strongly action and this can be demonstrated by the pair, then it does not suggest pulling the double.
So the pair must demonstrate that their agreements are that a double here says I want to bid 4♠, but I double in case you have a penalty pass.
The argument is - in a competitive auction always assume we are just trying to stop them making 110 in a major and not trying for game.
I have recently had a takeout of a slow double rolled back, as it was assumed that the slowness of the double made it less likely that the double was for penalties. The problem that I see is defining what the UI demonstrably suggests, taking into account the skills of the players concerned.
In an ideal world we would all manage a uniform tempo, as Michael Rosenberg argued so well in hos book.
In the world we currently live in I think that directors and committees do a good job of defining what are logical alternatives, and usually take into account the skill level of the players involved. They do a less good job of considering what is demonstrably suggested by the UI.
What did the bid of 3♥ mean?
If this meant that the defenders had more information than at other tables, then the comparison with the 11 other declarers playing on a ♠ lead is not valid.
IF they stop in 3♥ at red, they usually do not think they have game. Then it is quite likely that 3♥ will not make either.
No squeeze possible after Diamond lead.
Without Diamond lead we add a little bit (less than half the remaining chances as it needs long spades with longs hearts).
There is a reason to underlead the A♠. You assume to beat the contract that you need 1 ♠ trick and 2 red suit tricks.
So underleading the A♠ beats it whenever it can be beaten and leading the A♠ beats it only if partner has ♥.
Of course I can bid 4♥ if I believe 75% of my peers would do so. It would just get rolled back by the TD.
I think that this is all about full disclosure. The apponents are allowed to know what to expect.
After 1♥ (pass) 2♥ (pass) I made a Long suit trial bid of 3♣ with a short suit to try to induce a trump lead.
Now we do not describe our long suit trial bid as showing something like Axx, but as asking partner to evaluate his hand opposite a holding of Axx.
So Oren should be describing his 1NT opening as 15-17 with frequent upgrades and non-standard distributions. This is fair.
It is important to know if the 10 could be from K10. If so I play the Queen, if not the Ace.
As far as I know, we do not play with screens on BBO ….
Would 2♠ over a normal 2♣ overcall have been forcing?
Still I think partner has shown forcing with ♠, so he will get to play 8♠.
This auction has been described by Kit Woolsey.
♦ + another. Double is ♥ + ♣ or takeout.
What is this 3!S for you?
I play this as 6♥, 3NT shows the ♠ stopper without ♣ stopper and 3♥ ♣ stopper which leave room for 3♠ to ask for the ♠ stopper.


Romero and AUX present a night of performance and film with esoteric performance actions from Bastis with a film by Vox X artist Cudelice Brazelton.
Fresh off his exhibition at Catherine Bastide gallery in Brussels, Sculptor Nick Bastis continues his exploration of speaking and absence with a new video and performance about ventriloquism.
Noah Furman (artist) born 1984, Chicago, IL. Hunter college MFA expected may 2015. Works in painting, sculpture, and performance. Currently investigating death, the prone body, the floor, the unconscious, the voice, and light.
Cudelice Brazelton who exhibited in VOX X: Present Tense returns with a new series of video works that elaborate upon his work with black male tropes in society and art.
Nick Bastis (MFA, 2013, University of Chicago), born 1985. Currently based between Brussels, BE and Vilnius, LT. Works recently shown at the Museum of Contemporary Photography (Chicago, US), Fluxia (Milan, IT) and Objectif (Antwerp, BE), upcoming shows at Regards (Chicago, US), Podium (Olso, NO), Kunsthalle Athena (Athens, GR), Chapter NY (New York City, US).
and subcultures. Brazelton was in our annual juried exhibition VOX X: Present Tense at Vox Populi in PhIladelphia, Pennsylvania, and attended ACRE in the summer of 2014. Upcomingshows include a group exhibition in The Bike Room at Nancy Lu Rosenheim in 2015.