some spell-checking

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Hugh Burton 2020-11-28 16:56:27 +00:00
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@ -1137,7 +1137,7 @@ This analysis highlights the importance of the primary critical point in control
regardless of whether this point is inside or outside the complex unit circle. \cite{Handy_1985,Olsen_2000} regardless of whether this point is inside or outside the complex unit circle. \cite{Handy_1985,Olsen_2000}
%======================================= %=======================================
\subsection{The M{\o}ller--Plesset Critical Point} \subsection{M{\o}ller--Plesset Critical Point}
\label{sec:MP_critical_point} \label{sec:MP_critical_point}
%======================================= %=======================================
@ -1146,9 +1146,9 @@ In the early 2000's, Stillinger reconsidered the mathematical origin behind the
sign alternation.\cite{Stillinger_2000} sign alternation.\cite{Stillinger_2000}
This type of convergence behaviour corresponds to Cremer and He's class B systems with closely spaced This type of convergence behaviour corresponds to Cremer and He's class B systems with closely spaced
electron pairs and includes \ce{Ne}, \ce{HF}, \ce{F-}, and \ce{H2O}.\cite{Cremer_1996} electron pairs and includes \ce{Ne}, \ce{HF}, \ce{F-}, and \ce{H2O}.\cite{Cremer_1996}
Stillinger proposed that the divergence of these series arise from a dominant singularity Stillinger proposed that these series diverge due to a dominant singularity
on the negative real $\lambda$ axis, corresponding to a multielectron autoionisation threshold.\cite{Stillinger_2000} on the negative real $\lambda$ axis, corresponding to a multielectron autoionisation threshold.\cite{Stillinger_2000}
To understand Stillinger's argument, consider the paramterised MP Hamiltonian in the form To understand Stillinger's argument, consider the parametrised MP Hamiltonian in the form
\begin{multline} \begin{multline}
\label{eq:HamiltonianStillinger} \label{eq:HamiltonianStillinger}
\hH(\lambda) = \hH(\lambda) =
@ -1164,7 +1164,7 @@ The mean-field potential $v^{\text{HF}}$ essentially represents a negatively cha
controlled by the extent of the HF orbitals, usually located close to the nuclei. controlled by the extent of the HF orbitals, usually located close to the nuclei.
When $\lambda$ is negative, the mean-field potential becomes increasingly repulsive, while the explicit two-electron When $\lambda$ is negative, the mean-field potential becomes increasingly repulsive, while the explicit two-electron
Coulomb interaction becomes attractive. Coulomb interaction becomes attractive.
There is therefore a critical value $\lc < 0$ where it becomes energetically favourable for the electrons There is therefore a negative critical value $\lc$ where it becomes energetically favourable for the electrons
to dissociate and form a bound cluster at an infinite separation from the nuclei.\cite{Stillinger_2000} to dissociate and form a bound cluster at an infinite separation from the nuclei.\cite{Stillinger_2000}
This autoionisation effect is closely related to the critial point for electron binding in two-electron This autoionisation effect is closely related to the critial point for electron binding in two-electron
atoms (see Ref.~\onlinecite{Baker_1971}). atoms (see Ref.~\onlinecite{Baker_1971}).
@ -1174,9 +1174,9 @@ processes.\cite{Sergeev_2005}
% CLASSIFICATIONS BY GOODSOON AND SERGEEV % CLASSIFICATIONS BY GOODSOON AND SERGEEV
To further develop the link between the critical point and types of MP convergence, Sergeev and Goodson investigated To further develop the link between the critical point and types of MP convergence, Sergeev and Goodson investigated
the relationship with the location of the dominant singularity that controls the radius of convergence.\cite{Goodson_2004} the relationship with the location of the dominant singularity that controls the radius of convergence.\cite{Goodson_2004}
They demonstrated that the dominant singularity in class A corresponds to a dominant EP with a positive real component, They demonstrated that the dominant singularity in class A systems corresponds to a dominant EP with a positive real component,
with the magnitude of the imaginary component controlling the oscillations in the signs of the MP with the magnitude of the imaginary component controlling the oscillations in the signs of successive MP
term.\cite{Goodson_2000a,Goodson_2000b} terms.\cite{Goodson_2000a,Goodson_2000b}
In contrast, class B systems correspond to a dominant singularity on the negative real $\lambda$ axis representing In contrast, class B systems correspond to a dominant singularity on the negative real $\lambda$ axis representing
the MP critical point. the MP critical point.
The divergence of class B systems, which contain closely spaced electrons (\eg, \ce{F-}), can then be understood as the The divergence of class B systems, which contain closely spaced electrons (\eg, \ce{F-}), can then be understood as the
@ -1187,15 +1187,15 @@ and ii) $\beta$ singularities which have very small imaginary parts.\cite{Goodso
% RELATIONSHIP TO BASIS SET SIZE % RELATIONSHIP TO BASIS SET SIZE
The existence of the MP critical point can also explain why the divergence observed by Olsen \etal\ in the \ce{Ne} atom The existence of the MP critical point can also explain why the divergence observed by Olsen \etal\ in the \ce{Ne} atom
and \ce{HF} molecule occured when diffuse basis functions were included.\cite{Olsen_1996} and \ce{HF} molecule occurred when diffuse basis functions were included.\cite{Olsen_1996}
Clearly diffuse basis functions are required for the electrons to dissociate from the nuclei, and indeed using Clearly diffuse basis functions are required for the electrons to dissociate from the nuclei, and indeed using
only compact basis functions causes the critical point to disappear. only compact basis functions causes the critical point to disappear.
While a finite basis can only predict complex-conjugate branch point singularities, the critical point is modelled While a finite basis can only predict complex-conjugate branch point singularities, the critical point is modelled
by a cluster of sharp avoided crossings between the ground state and high-lying excited states.\cite{Sergeev_2005} by a cluster of sharp avoided crossings between the ground state and high-lying excited states.\cite{Sergeev_2005}
Alternatively, Sergeev \etal\ demonstrated that the inclusion of a ``ghost'' atom also Alternatively, Sergeev \etal\ demonstrated that the inclusion of a ``ghost'' atom also
allows the formation of the critical point as the electrons form a bound cluster occuping the ghost atom orbitals.\cite{Sergeev_2005} allows the formation of the critical point as the electrons form a bound cluster occupying the ghost atom orbitals.\cite{Sergeev_2005}
This effect explains the origin of the divergence in the \ce{HF} molecule as the \ce{F} valence electrons jump to \ce{H} This effect explains the origin of the divergence in the \ce{HF} molecule as the fluorine valence electrons jump to hydrogen at
for a sufficiently negative $\lambda$ value.\cite{Sergeev_2005} a sufficiently negative $\lambda$ value.\cite{Sergeev_2005}
Furthermore, the two-state model of Olsen \etal{}\cite{Olsen_2000} was simply too minimal to understand the complexity of Furthermore, the two-state model of Olsen \etal{}\cite{Olsen_2000} was simply too minimal to understand the complexity of
divergences caused by the MP critical point. divergences caused by the MP critical point.
@ -1220,12 +1220,12 @@ divergences caused by the MP critical point.
When a Hamiltonian is parametrised by a variable such as $\lambda$, the existence of abrupt changes in the When a Hamiltonian is parametrised by a variable such as $\lambda$, the existence of abrupt changes in the
eigenstates as a function of $\lambda$ indicate the presence of a zero-temperature quantum phase transition (QPT).% eigenstates as a function of $\lambda$ indicate the presence of a zero-temperature quantum phase transition (QPT).%
\cite{Heiss_1988,Heiss_2002,Borisov_2015,Sindelka_2017,CarrBook,Vojta_2003,SachdevBook,GilmoreBook} \cite{Heiss_1988,Heiss_2002,Borisov_2015,Sindelka_2017,CarrBook,Vojta_2003,SachdevBook,GilmoreBook}
As an avoided crossing becomes increasingly sharp, the corresponding EPs move increasingly close to the real axis, eventually forming a critical point. Meanwhile, as an avoided crossing becomes increasingly sharp, the corresponding EPs move increasingly close to the real axis, eventually forming a critical point.
The existence of an EP \emph{on} the real axis is therefore diagnostic of a QPT.\cite{Cejnar_2005, Cejnar_2007a} The existence of an EP \emph{on} the real axis is therefore diagnostic of a QPT.\cite{Cejnar_2005, Cejnar_2007a}
Since the MP critical point corresponds to a singularity on the real $\lambda$ axis, it can immediately be Since the MP critical point corresponds to a singularity on the real $\lambda$ axis, it can immediately be
recognised a QPT within the perturbation theory approximation. recognised as a QPT within the perturbation theory approximation.
However, a conventional QPT can only occur in the thermodynamic limit, which here is analogous to the complete However, a conventional QPT can only occur in the thermodynamic limit, which here is analogous to the complete
basis set limit in our case.\cite{Kais_2006} basis set limit.\cite{Kais_2006}
The MP critical point $\beta$ singularity in a finite basis must therefore be modelled by pairs of EPs The MP critical point $\beta$ singularity in a finite basis must therefore be modelled by pairs of EPs
that tend towards the real axis, exactly as described by Sergeev \etal\cite{Sergeev_2005} that tend towards the real axis, exactly as described by Sergeev \etal\cite{Sergeev_2005}
In contrast, $\alpha$ singularities correspond to large avoided crossings that are indicative of low-lying excited In contrast, $\alpha$ singularities correspond to large avoided crossings that are indicative of low-lying excited