diff --git a/Manuscript/EPAWTFT.tex b/Manuscript/EPAWTFT.tex index 9af5c45..9d8bed7 100644 --- a/Manuscript/EPAWTFT.tex +++ b/Manuscript/EPAWTFT.tex @@ -104,6 +104,8 @@ \renewcommand{\i}{\mathrm{i}} % Imaginary unit \newcommand{\e}{\mathrm{e}} % Euler number \newcommand{\rc}{r_{\text{c}}} +\newcommand{\lc}{\lambda_{\text{c}}} +\newcommand{\lep}{\lambda_{\text{EP}}} % Blackboard bold \newcommand{\bbR}{\mathbb{R}} @@ -607,61 +609,71 @@ role of \textit{quasi}-EPs in determining the behaviour of the HF approximation. \subsection{M{\o}ller-Plesset perturbation theory} %=====================================================% -The HF Hamiltonian \eqref{eq:HFHamiltonian} can be used as the zeroth-order Hamiltonian of Eq.~\eqref{eq:SchrEq-PT}. This partitioning of the Hamiltonian leads to the so-called M{\o}ller-Plesset (MP) perturbation theory. \cite{Moller_1934} -The discovery of a partitioning of the Hamiltonian that allowed chemists to recover a large chunck of the correlation energy (\ie, the difference between the exact energy and the Hartree-Fock energy) using perturbation theory has been a major step in the development of post-HF methods. -This yields +In electronic structure, the HF Hamiltonian \eqref{eq:HFHamiltonian} is often used as the zeroth-order Hamiltonian +to define M\o{}ller--Plesset (MP) perturbation theory.\cite{Moller_1934} +This approach can recover a large proportion of the electron correlation energy,\cite{Lowdin_1955} +and provides the foundation for numerous post-HF approximations. +With the MP partitioning, the parametrised perturbation Hamiltonian becomes \begin{multline}\label{eq:MPHamiltonian} \hH(\lambda) = - \sum_{i}^{N} \Bigg[ + \sum_{i}^{N} \Bigg( -\frac{\grad_i^2}{2} - \sum_{A}^{M} \frac{Z_A}{\abs{\vb{r}_i-\vb{R}_A}} \\ + (1-\lambda) v^{\text{HF}}(\vb{x}_i) + \lambda\sum_{i 1$) and $4.5$ (where $r_c < 1$) is illustrated in Fig.~\ref{subfig:RMP_cvg}. -The Riemann surfaces associated with the exact energy of the RMP Hamiltonian \eqref{eq:H_RMP} are also represented for these two values of $U/t$ (see Figs.~\ref{subfig:RMP_3.5} and \ref{subfig:RMP_4.5}). -From these, one \titou{clearly?} sees that the EP is outside (inside) the (pink) cylinder of unit radius for $U/t = 3.5$ ($4.5$), -and the centre graph of Fig.~\ref{fig:RMP} evidences the convergent (divergent) nature of the RMP series. -Interestingly, one can show that the convergent and divergent series start to differ at fourth order. +%with +%\begin{equation} +% E_{\text{MP}n}(\lambda) = \sum_{k=0}^n E_\text{MP}^{(k)} \lambda^k. +%\end{equation} + +\hugh{The RMP series is convergent for $U = 3.5\,t$ with $\rc > 1$, as illustrated for the individual terms at each order +of perturbation in Fig.~\ref{subfig:RMP_cvg}. +In contrast, for $U = 4.5t$ one finds $\rc < 1$, and the RMP series becomes divergent. +The corresponding Riemann surfaces for $U = 3.5\,t$ and $4.5\,t$ are shown in Figs.~\ref{subfig:RMP_3.5} and +\ref{subfig:RMP_4.5} respectively, with the single EP at $\lep$ (black dot) and the radius of convergence indicated +by the vertical cylinder of unit radius. +In the divergent case, the $\lep$ lies inside this cylinder of convergence, while in the convergent case $\lep$ can bee +seen outside this cylinder. +The convergent and divergent series start to differ at fourth order, corresponding to the lowest-order contribution +from the single excitations.\cite{Lepetit_1998} +This divergent behaviour might therefore be attributed to the need for the single excitations to focus on correcting +the structure of the reference orbitals rather than capturing the correlation energy. +} %%% FIG 2 %%% \begin{figure*} @@ -764,6 +790,12 @@ An EP this close to the radius of convergence gives an increasingly slow converg \label{fig:UMP}} \end{figure*} +\hugh{(\textbf{HGAB}: Lets keep all the MP discussion together and add this note here)} +Obviously, although practically convenient for electronic structure calculations, the MP partitioning is not the only possibility, and alternative partitioning have been proposed in the literature: +i) the Epstein-Nesbet (EN) partitioning which consists in taking the diagonal elements of $\hH$ as the zeroth-order Hamiltonian. \cite{Nesbet_1955,Epstein_1926} +Hence, the off-diagonal elements of $\hH$ are the perturbation operator, +ii) the weak correlation partitioning in which the one-electron part is consider as the unperturbed Hamiltonian $\hH^{(0)}$ and the two-electron part is the perturbation operator $\hV$, and +iii) the strong coupling partitioning where the two operators are inverted compared to the weak correlation partitioning. \cite{Seidl_2018} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%% \section{Historical overview}