diff --git a/Manuscript/EPAWTFT.tex b/Manuscript/EPAWTFT.tex index 7029826..db2858c 100644 --- a/Manuscript/EPAWTFT.tex +++ b/Manuscript/EPAWTFT.tex @@ -144,7 +144,7 @@ \begin{abstract} In this review, we explore the extension of quantum chemistry in the complex plane and its link with perturbation theory. We observe that the physics of a quantum system is intimately connected to the position of energy singularities in the complex plane, known as exceptionnal points. -After a presentation of the fundamental notions of quantum chemistry in the complex plane, such as the mean-field Hartree-Fock approximation and Rayleigh-Schr\"odinger perturbation theory, and their illustration with the ubiquitous (symmetric) Hubbard dimer at half filling, we provide a historical overview of the various research activities that have been performed on the physics of singularities. +After a presentation of the fundamental notions of quantum chemistry in the complex plane, such as the mean-field Hartree--Fock approximation and Rayleigh-Schr\"odinger perturbation theory, and their illustration with the ubiquitous (symmetric) Hubbard dimer at half filling, we provide a historical overview of the various research activities that have been performed on the physics of singularities. In particular, we highlight the seminal work of several research groups on the convergence behaviour of perturbative series obtained within M{\o}ller--Plesset perturbation theory and its apparent link with quantum phase transitions. \end{abstract} @@ -418,12 +418,12 @@ Later we will demonstrate how the choice of reference Hamiltonian controls the p ultimately determines the convergence properties of the perturbation series. %===========================================% -\subsection{Hartree-Fock Theory} +\subsection{Hartree--Fock Theory} \label{sec:HF} %===========================================% % SUMMARY OF HF -In the Hartree-Fock (HF) approximation, the many-electron wave function is approximated as a single Slater determinant $\Psi^{\text{HF}}(\vb{x}_1,\ldots,\vb{x}_N)$, where $\vb{x} = (\sigma,\vb{r})$ is a composite vector gathering spin and spatial coordinates. +In the Hartree--Fock (HF) approximation, the many-electron wave function is approximated as a single Slater determinant $\Psi^{\text{HF}}(\vb{x}_1,\ldots,\vb{x}_N)$, where $\vb{x} = (\sigma,\vb{r})$ is a composite vector gathering spin and spatial coordinates. This Slater determinant is defined as an antisymmetric combination of $\Ne$ (real-valued) occupied one-electron spin-orbitals $\phi_p(\vb{x})$, which are, by definition, eigenfunctions of the one-electron Fock operator \begin{equation}\label{eq:FockOp} \Hat{f}(\vb{x}) \phi_p(\vb{x}) = \qty[ \Hat{h}(\vb{x}) + \Hat{v}_\text{HF}(\vb{x}) ] \phi_p(\vb{x}) = \epsilon_p \phi_p(\vb{x}). @@ -483,7 +483,7 @@ However, by allowing different orbitals for different spins, the UHF is no longe the total spin $\hat{\mathcal{S}}^2$ operator, leading to ``spin-contamination'' in the wave function. %================================================================% -\subsection{Hartree-Fock in the Hubbard Dimer} +\subsection{Hartree--Fock in the Hubbard Dimer} \label{sec:HF_hubbard} %================================================================% @@ -628,7 +628,7 @@ via a stationary path of HF solutions. This novel approach to identifying excited-state wave functions demonstrates the fundamental role of \textit{quasi}-EPs in determining the behaviour of the HF approximation. -%\titou{In a recent paper, \cite{Burton_2019} using holomorphic Hartree-Fock (h-HF) \cite{Hiscock_2014,Burton_2018,Burton_2016} as an analytic continuation of conventional HF theory, we have demonstrated, on a simple model, that one can interconvert states of different symmetries and natures by following well-defined contours in the complex $\lambda$-plane, where $\lambda$ is the strength of the electron-electron interaction (see Fig.~\ref{fig:iAC}). +%\titou{In a recent paper, \cite{Burton_2019} using holomorphic Hartree--Fock (h-HF) \cite{Hiscock_2014,Burton_2018,Burton_2016} as an analytic continuation of conventional HF theory, we have demonstrated, on a simple model, that one can interconvert states of different symmetries and natures by following well-defined contours in the complex $\lambda$-plane, where $\lambda$ is the strength of the electron-electron interaction (see Fig.~\ref{fig:iAC}). %In particular, by slowly varying $\lambda$ in a similar (yet different) manner to an adiabatic connection in density-functional theory, \cite{Langreth_1975,Gunnarsson_1976,Zhang_2004} one can ``morph'' a ground-state wave function into an excited-state wave function via a stationary path of HF solutions. \cite{Seidl_2018} %In such a way, we could obtain a doubly-excited state wave function starting from the ground state wave function, a process which is not as easy as one might think. \cite{Gilbert_2008,Thom_2008,Shea_2018} %One of the fundamental discovery we made was that Coulson-Fischer points (where multiple symmetry-broken solutions coalesce) play a central role and can be classified as \textit{quasi}-exceptional points, as the wave functions do not become self-orthogonal. @@ -637,7 +637,7 @@ role of \textit{quasi}-EPs in determining the behaviour of the HF approximation. %Through the introduction of non-Hermiticity, we have provided a more general framework in which the complex and diverse characteristics of multiple solutions can be explored and understood.} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -\section{M{\o}ller--Plesset Perturbation Theory in the Complex Plane} +\section{M{\o}ller--Plesset Theory in the Complex Plane} \label{sec:MP} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% @@ -714,7 +714,7 @@ their relative strengths and weaknesses for various situations, we will restrict to the convergence properties of the MP expansion. %=====================================================% -\subsection{Early Investigations into M{\o}ller--Plesset Convergence} % in Molecular Systems} +\subsection{Early Studies of M{\o}ller--Plesset Convergence} % in Molecular Systems} %=====================================================% % GENERAL DESIRE FOR WELL-BEHAVED CONVERGENCE AND LOW-ORDER TERMS @@ -1010,7 +1010,7 @@ very slowly as the perturbation order is increased. %==========================================% -\subsection{Classifying Types of Convergence Behaviour} % Further insights from a two-state model} +\subsection{Classifying Types of Convergence} % Behaviour} % Further insights from a two-state model} %==========================================% % CREMER AND HE @@ -1137,91 +1137,157 @@ 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} %======================================= -\subsection{The singularity structure} +\subsection{The M{\o}ller--Plesset Critical Point} \label{sec:MP_critical_point} %======================================= -In the 2000's, Sergeev and Goodson \cite{Sergeev_2005, Sergeev_2006} analysed this problem from a more mathematical point of view by looking at the whole singularity structure where Olsen and collaborators were trying to find the dominant singularity causing the divergence. \cite{Olsen_1996,Olsen_2000,Olsen_2019} -They regrouped singularities in two classes: i) $\alpha$ singularities which have ``large'' imaginary parts, and ii) $\beta$ singularities which have very small imaginary parts. -Singularities of $\alpha$-type are related to large avoided crossing between the ground and low-lying excited states, whereas $\beta$ singularities come from a sharp avoided crossing between the ground state and a highly diffuse state. -They succeeded to explain the divergence of the series caused by $\beta$ singularities following previous work by Stillinger. \cite{Stillinger_2000} - -To understand the convergence properties of the perturbation series at $\lambda=1$, one must look at the whole complex plane, in particular, for negative (\ie, real) values of $\lambda$. -If $\lambda$ is negative, the Coulomb interaction becomes attractive but the mean field (which has been computed at $\lambda = 1$) remains repulsive as it is proportional to $(1-\lambda)$: +% STILLINGER INTRODUCES THE CRITICAL POINT +\hugh{% +In the early 2000's, Stillinger reconsidered the mathematical origin behind the divergent series with odd-even +sign alternation.\cite{Stillinger_2000} +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} +Stillinger proposed that the divergence of these series occurs arise from a dominant singularity +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 \begin{multline} \label{eq:HamiltonianStillinger} \hH(\lambda) = - \sum_{i}^{n} \Bigg[ + \sum_{i}^{\Ne} \Bigg[ \overbrace{-\frac{1}{2}\grad_i^2 - - \sum_{A}^{N} \frac{Z_A}{\abs{\vb{r}_i-\vb{R}_A}}}^{\text{independent of $\lambda$}} + - \sum_{A}^{\Nn} \frac{Z_A}{\abs{\vb{r}_i-\vb{R}_A}}}^{\text{independent of $\lambda$}} \\ + \underbrace{(1-\lambda)v^{\text{HF}}(\vb{x}_i)}_{\text{repulsive for $\lambda < 1$}} - + \underbrace{\lambda\sum_{i Resummation: + +Can use either Pade or quadratic approximants. Pade can't describe branch points, so quadratic are more +suitable. Quadratics fit more complicated branch points using clusters of square-root branch points. + +> Examples + +They use these approximants to identify the dominant singularities. As expected, they find the dominant +singularity in the Class A systems lie on the positive half plane with relatively large imaginary component. + +BH is classic Class A, and F- is a classic Class B. + +For Class B, the quadratic approximants gain an imaginary part beyond the critical point. The rational +approximant maps the branch point using alternating zeros and poles along the real axis. The quadratic +approximants cluster a number of branch points around the critical point, suggesting a fundamental difference +to a branch point in the positive plane. + +From this analysis, all complex conjugate branch points are defined as `class \alpha', and the critical +point is defined as `class \beta'. + +Better to actually classify with respect to the dominant singularity in the negative/positive half planes +to give eg alpha/alpha .... + +Sergeev, Goodson, Wheeler, and Allen, JCP (2005): +------------------------------------------------- +Olsen showed that the F- series is divergent with diffuse functions, but convergent with compact functions. +This paper considers Stillinger's conjecture for the noble gases by analysing the singularity structure. + +Increasing Z increases barrier for the electrons to escape, but the well in the nuclear region narrows. +Eventually the electrons can escape by tunneling through the barrier. It is also possible to get a critical +point in the positive real z-axis corresponding to one-electron ionization. THIS would correspond to the +two-electron critical point. + +In a finite basis set, the singular (branch points) must occur in complex conjugate pairs. They show that +increasing the basis set size leads to a cluster of very tight avoided crossings for negative z. These +avoided crossings are modelling the continuum and the critical point. They add +a ghost atom to allow the electrons to dissociate, and show that these lead to greater clustering of +negative avoided crossings. This ghost atom can then be replaced by a real atom (eg Ne -> HF), and then +the valence electrons will jump to the hydrogen, leading to a critical point (as shown by a plot of the +dipole moment). These two systems therefore have similar convergence behaviour. Without this ghost atom, +one gets complete dissociation rather than an electron cluster formation. + +Indeed similar clustering is seen in the positive real z values, eg in Ar. The argument is that the valence +electrons are farther from the nucleus than in Ne, so the mean-field potential is less able to counter +the increased interelectron repulsion than in Ne. + +Analysis resolves a disagreement between Stillinger and Olsen. Olsen found Class B resulted in square-root +branch points, but this is only because the 2x2 matrix is insufficient. + +A key result from this paper is that critical points can also occur on the positive real axis, and these +correspond to one-electron ionisations. Origin is an avoided crossing with high-energy Rydberg state. + +Sergeev and Goodson, JCP (2006): +-------------------------------- +Further explore the singularity structure of a set of systems to classify using the alpha/beta scheme. + +Systems with a low-lying excited state that mixes strongly with the ground state, such that a +single-reference HF determinant gives a poor descriptions of the wave function, will have a class \alpha +singularity in the positive half plane slightly beyond the physical point z=1. + +Goodson and Sergeev, PLA (2006): +-------------------------------- +This paper considers how to understand the singularity structure using only up to MP4. Argument is that E_FCI(z) +must always have complex-conjugate branch points, so cannot accurately model the true critical point E(z). +Instead, it models these critical points with a cluster of square-root branch point pairs with small imaginary +components. (See Sergeev et al. 2005) + +This paper introduces further approximants to model these singularities using only MP4 information. It can +then consider larger systems. They also use some conformal mapping and other tricks to improve the representation +of the singularities and improve convergence. + +Herman and Hagedorn, IJQC (2008): +--------------------------------- +Consider convergence or divergence of MP is considered for two-electrons with variable nuclear charge. +In particular, they look to extend Goodson analysis to see how the singularity changes for increasingly more +exact Hamiltonians. + +They use a `delta-function model' for He-like atoms, where the delta functions replace the Coulomb potentials. +This is advantageous as the problem becomes one-dimensional. They introduce a second model for the e-e cluster. +The Stillinger critical point is then a point where the two energies cross. + +[ALL GETS A BIT INVOLVED... SKIPPING TO CONCLUSIONS...] + +[[TO BE HONEST, NOT SURE WHAT ALL THIS SHOWS...]] + + ++==========================================================+ +| Miscellaneous (or category currently unclear) | ++==========================================================+ +Fink, JCP (2016): +----------------- +