intro OK
This commit is contained in:
parent
6aab2922cf
commit
1f9cd08f39
@ -166,7 +166,7 @@ Each of these points is further illustrated with the ubiquitous Hubbard dimer at
|
||||
%%%%%%%%%%%%%%%%%%%%%%%
|
||||
|
||||
% SPIKE THE READER
|
||||
\hugh{Perturbation theory isn't usually considered in the complex plane.
|
||||
Perturbation theory isn't usually considered in the complex plane.
|
||||
Normally it is applied using real numbers as one of very few availabe tools for
|
||||
describing realistic quantum systems where exact solutions of the Schr\"odinger equation are impossible.\cite{Dirac_1929}
|
||||
In particular, time-independent Rayleigh--Schr\"odinger perturbation theory\cite{RayleighBook,Schrodinger_1926}
|
||||
@ -174,7 +174,6 @@ has emerged as an instrument of choice among the vast array of methods developed
|
||||
\cite{SzaboBook,JensenBook,CramerBook,HelgakerBook,ParrBook,FetterBook,ReiningBook}
|
||||
However, the properties of perturbation theory in the complex plane
|
||||
are essential for understanding the quality of perturbative approximations on the real axis.
|
||||
}
|
||||
|
||||
% Good old Schroedinger
|
||||
%The electronic Schr\"odinger equation,
|
||||
@ -196,19 +195,19 @@ are essential for understanding the quality of perturbative approximations on th
|
||||
% Moller-Plesset
|
||||
%\hugh{Accurately predicting the electronic energy is the primary focus of electronic structure theory, in
|
||||
%principle providing a fundamental understanding of chemical structure, bonding, and reactivity.
|
||||
\hugh{In electronic structure theory,} the workhorse of time-independent perturbation theory is M\o{}ller--Plesset (MP) %perturbation
|
||||
In electronic structure theory, the workhorse of time-independent perturbation theory is M\o{}ller--Plesset (MP) %perturbation
|
||||
theory,\cite{Moller_1934} which remains one of the most popular methods for computing the electron
|
||||
correlation energy.\cite{Wigner_1934,Lowdin_1958}
|
||||
%\trashHB{an old yet important concept, first introduced by Wigner \cite{Wigner_1934} and later defined by L\"owdin. \cite{Lowdin_1958}}
|
||||
This approach estimates the exact electronic energy by constructing a perturbative correction on top
|
||||
of a mean-field Hartree--Fock (HF) approximation.\cite{SzaboBook}
|
||||
The popularity of MP theory stems from its black-box nature, \hugh{size-extensivity,} and relatively low computational scaling,
|
||||
The popularity of MP theory stems from its black-box nature, size-extensivity, and relatively low computational scaling,
|
||||
making it easily applied in a broad range of molecular research.\cite{HelgakerBook}
|
||||
However, it is now widely recognised that the series of MP approximations (defined for a given perturbation
|
||||
order $n$ as MP$n$) can show erratic, slow, or divergent behaviour that limit its systematic improvability.%
|
||||
\cite{Laidig_1985,Knowles_1985,Handy_1985,Gill_1986,Laidig_1987,Nobes_1987,Gill_1988,Gill_1988a,Lepetit_1988}
|
||||
As a result, practical applications typically employ only the lowest-order MP2 approach, while
|
||||
the successive MP3, MP4, and MP5 (and higher \hugh{order}) terms are generally not considered to offer enough improvement
|
||||
the successive MP3, MP4, and MP5 (and higher order) terms are generally not considered to offer enough improvement
|
||||
to justify their increased cost.
|
||||
Turning the MP approximations into a convergent and
|
||||
systematically improvable series largely remains an open challenge.
|
||||
@ -269,16 +268,15 @@ In doing so, we will demonstrate how understanding the MP energy in the complex
|
||||
be harnessed to significantly improve estimates of the exact energy using only the lowest-order terms
|
||||
in the MP series.
|
||||
|
||||
\trashHB{The present review is organised as follows.}
|
||||
In Sec.~\ref{sec:EPs}, we introduce the key concepts such as Rayleigh-Schr\"odinger perturbation theory and the mean-field HF approximation, and discuss their \hugh{non-Hermitian} analytic continuation into the complex plane.
|
||||
In Sec.~\ref{sec:EPs}, we introduce the key concepts such as Rayleigh-Schr\"odinger perturbation theory and the mean-field HF approximation, and discuss their non-Hermitian analytic continuation into the complex plane.
|
||||
Section \ref{sec:MP} presents MP perturbation theory and we report a comprehensive historical overview of the research that
|
||||
has been performed on the physics of MP singularities.
|
||||
In Sec.~\ref{sec:Resummation}, we discuss several resummation techniques for improving the accuracy
|
||||
of low-order MP approximations, including Pad\'e and quadratic approximants.
|
||||
Finally, we draw our conclusions in Sec.~\ref{sec:ccl} \hugh{and highlight our perspective on directions for
|
||||
future research}.
|
||||
Finally, we draw our conclusions in Sec.~\ref{sec:ccl} and highlight our perspective on directions for
|
||||
future research.
|
||||
Throughout this review, we present illustrative and pedagogical examples based on the ubiquitous
|
||||
Hubbard dimer, \hugh{reinforcing} the amazing versatility of this powerful simplistic model.
|
||||
Hubbard dimer, reinforcing the amazing versatility of this powerful simplistic model.
|
||||
|
||||
%%%%%%%%%%%%%%%%%%%%%%%
|
||||
\section{Exceptional Points in Electronic Structure}
|
||||
|
Loading…
Reference in New Issue
Block a user