From 9b974931e872bcdb10088511025fd51893075f5b Mon Sep 17 00:00:00 2001 From: Pierre-Francois Loos Date: Thu, 30 May 2019 10:05:22 +0200 Subject: [PATCH] SI --- Manuscript/Ex-srDFT.tex | 2 +- Manuscript/SI/Ex-srDFT-SI.tex | 292 ++++++++++++++++++++++++++++++++++ 2 files changed, 293 insertions(+), 1 deletion(-) create mode 100644 Manuscript/SI/Ex-srDFT-SI.tex diff --git a/Manuscript/Ex-srDFT.tex b/Manuscript/Ex-srDFT.tex index 5a80325..52b32ec 100644 --- a/Manuscript/Ex-srDFT.tex +++ b/Manuscript/Ex-srDFT.tex @@ -333,7 +333,7 @@ This computationally-lighter functional will be refered to as PBE. In the present study, we compute the ground- and excited-state energies, one-electron and on-top densities with a selected CI method known as CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively). \cite{HurMalRan-JCP-73, GinSceCaf-CJC-13, GinSceCaf-JCP-15} The total energy of each state is obtained via an efficient extrapolation procedure of the sCI energies designed to reach near-FCI accuracy. \cite{QP2} These energies will be labeled exFCI in the following. -We refer the interested reader to Refs.~\onlinecite{HolUmrSha-JCP-17, SceGarCafLoo-JCTC-18, LooSceBloGarCafJac-JCTC-18, SceBenJacCafLoo-JCP-18, LooBogSceCafJAc-JCTC-19, QP2} for more details. +We refer the interested reader to Refs.~\onlinecite{HolUmrSha-JCP-17, SceGarCafLoo-JCTC-18, LooSceBloGarCafJac-JCTC-18, SceBenJacCafLoo-JCP-18, LooBogSceCafJac-JCTC-19, QP2} for more details. The one-electron and on-top densities are computed from a very large CIPSI expansion containing several million determinants. All the RS-DFT and exFCI calculations have been performed with {\QP}. \cite{QP2} For the numerical quadratures, we employ the SG-2 grid. \cite{DasHer-JCC-17} diff --git a/Manuscript/SI/Ex-srDFT-SI.tex b/Manuscript/SI/Ex-srDFT-SI.tex new file mode 100644 index 0000000..fd9c350 --- /dev/null +++ b/Manuscript/SI/Ex-srDFT-SI.tex @@ -0,0 +1,292 @@ +\documentclass[aip,jcp,reprint,onecolumn,noshowkeys]{revtex4-1} +\usepackage{graphicx,dcolumn,bm,xcolor,microtype,multirow,amscd,amsmath,amssymb,amsfonts,physics,mhchem,longtable} + +\usepackage{natbib} +\bibliographystyle{achemso} +\AtBeginDocument{\nocite{achemso-control}} +\usepackage{mathpazo,libertine} + +\usepackage{hyperref} +\hypersetup{ + colorlinks=true, + linkcolor=blue, + filecolor=blue, + urlcolor=blue, + citecolor=blue +} +\newcommand{\alert}[1]{\textcolor{red}{#1}} +\definecolor{darkgreen}{HTML}{009900} +\usepackage[normalem]{ulem} +\newcommand{\titou}[1]{\textcolor{black}{#1}} +\newcommand{\jt}[1]{\textcolor{purple}{#1}} +\newcommand{\manu}[1]{\textcolor{darkgreen}{#1}} +\newcommand{\toto}[1]{\textcolor{brown}{#1}} +\newcommand{\trashPFL}[1]{\textcolor{red}{\sout{#1}}} +\newcommand{\trashJT}[1]{\textcolor{purple}{\sout{#1}}} +\newcommand{\trashMG}[1]{\textcolor{darkgreen}{\sout{#1}}} +\newcommand{\trashAS}[1]{\textcolor{brown}{\sout{#1}}} +\newcommand{\MG}[1]{\manu{(\underline{\bf MG}: #1)}} +\newcommand{\JT}[1]{\juju{(\underline{\bf JT}: #1)}} +\newcommand{\PFL}[1]{\titou{(\underline{\bf PFL}: #1)}} +\newcommand{\AS}[1]{\toto{(\underline{\bf TOTO}: #1)}} + +\usepackage{hyperref} +\hypersetup{ + colorlinks=true, + linkcolor=blue, + filecolor=blue, + urlcolor=blue, + citecolor=blue +} +\newcommand{\mc}{\multicolumn} +\newcommand{\fnm}{\footnotemark} +\newcommand{\fnt}{\footnotetext} +\newcommand{\tabc}[1]{\multicolumn{1}{c}{#1}} +\newcommand{\SI}{\textcolor{blue}{supporting information}} +\newcommand{\QP}{\textsc{quantum package}} + +% second quantized operators +\newcommand{\ai}[1]{\hat{a}_{#1}} +\newcommand{\aic}[1]{\hat{a}^{\dagger}_{#1}} + +% units +\newcommand{\IneV}[1]{#1 eV} +\newcommand{\InAU}[1]{#1 a.u.} +\newcommand{\InAA}[1]{#1 \AA} +\newcommand{\kcal}{kcal/mol} + +% methods +\newcommand{\D}{\text{D}} +\newcommand{\T}{\text{T}} +\newcommand{\Q}{\text{Q}} +\newcommand{\X}{\text{X}} +\newcommand{\UEG}{\text{UEG}} +\newcommand{\HF}{\text{HF}} +\newcommand{\ROHF}{\text{ROHF}} +\newcommand{\LDA}{\text{LDA}} +\newcommand{\PBE}{\text{PBE}} +\newcommand{\FCI}{\text{FCI}} +\newcommand{\CBS}{\text{CBS}} +\newcommand{\exFCI}{\text{exFCI}} +\newcommand{\CCSDT}{\text{CCSD(T)}} +\newcommand{\lr}{\text{lr}} +\newcommand{\sr}{\text{sr}} + +\newcommand{\Ne}{N} +\newcommand{\NeUp}{\Ne^{\uparrow}} +\newcommand{\NeDw}{\Ne^{\downarrow}} +\newcommand{\Nb}{N_{\Bas}} +\newcommand{\Ng}{N_\text{grid}} +\newcommand{\nocca}{n_{\text{occ}^{\alpha}}} +\newcommand{\noccb}{n_{\text{occ}^{\beta}}} + +\newcommand{\n}[2]{n_{#1}^{#2}} +\newcommand{\Ec}{E_\text{c}} +\newcommand{\E}[2]{E_{#1}^{#2}} +\newcommand{\DE}[2]{\Delta E_{#1}^{#2}} +\newcommand{\bE}[2]{\Bar{E}_{#1}^{#2}} +\newcommand{\DbE}[2]{\Delta \Bar{E}_{#1}^{#2}} +\newcommand{\bEc}[1]{\Bar{E}_\text{c,md}^{#1}} +\newcommand{\e}[2]{\varepsilon_{#1}^{#2}} +\newcommand{\be}[2]{\Bar{\varepsilon}_{#1}^{#2}} +\newcommand{\bec}[1]{\Bar{e}^{#1}} +\newcommand{\wf}[2]{\Psi_{#1}^{#2}} +\newcommand{\W}[2]{W_{#1}^{#2}} +\newcommand{\w}[2]{w_{#1}^{#2}} +\newcommand{\hn}[2]{\Hat{n}_{#1}^{#2}} +\newcommand{\rsmu}[2]{\mu_{#1}^{#2}} +\newcommand{\V}[2]{V_{#1}^{#2}} +\newcommand{\SO}[2]{\phi_{#1}(\br{#2})} + +\newcommand{\tX}{\text{X}} + +% basis sets +\newcommand{\Bas}{\mathcal{B}} +\newcommand{\BasFC}{\mathcal{A}} +\newcommand{\FC}{\text{FC}} +\newcommand{\occ}{\text{occ}} +\newcommand{\virt}{\text{virt}} +\newcommand{\val}{\text{val}} +\newcommand{\Cor}{\mathcal{C}} + +% operators +\newcommand{\hT}{\Hat{T}} +\newcommand{\hWee}[1]{\Hat{W}_\text{ee}^{#1}} +\newcommand{\updw}{\uparrow\downarrow} +\newcommand{\f}[2]{f_{#1}^{#2}} +\newcommand{\Gam}[2]{\Gamma_{#1}^{#2}} + +% coordinates +\newcommand{\br}[1]{\mathbf{r}_{#1}} +\newcommand{\dbr}[1]{d\br{#1}} + +\newcommand{\ra}{\rightarrow} + +% frozen core +\newcommand{\WFC}[2]{\widetilde{W}_{#1}^{#2}} +\newcommand{\fFC}[2]{\widetilde{f}_{#1}^{#2}} +\newcommand{\rsmuFC}[2]{\widetilde{\mu}_{#1}^{#2}} +\newcommand{\nFC}[2]{\widetilde{n}_{#1}^{#2}} + + +% energies +\newcommand{\EHF}{E_\text{HF}} +\newcommand{\EPT}{E_\text{PT2}} +\newcommand{\EFCI}{E_\text{FCI}} +\newcommand{\EsCI}{E_\text{sCI}} +\newcommand{\EDMC}{E_\text{DMC}} +\newcommand{\EexFCI}{E_\text{exFCI}} +\newcommand{\EexDMC}{E_\text{exDMC}} +\newcommand{\Ead}{\Delta E_\text{ad}} +\newcommand{\Eabs}{\Delta E_\text{abs}} + +\newcommand{\ex}[4]{$^{#1}#2_{#3}^{#4}$} + +\newcommand{\pis}{\pi^\star} +\newcommand{\si}{\sigma} +\newcommand{\sis}{\sigma^\star} + + +\newcommand{\LCPQ}{Laboratoire de Chimie et Physique Quantiques (UMR 5626), Universit\'e de Toulouse, CNRS, UPS, France} +\newcommand{\LCT}{Laboratoire de Chimie Th\'eorique (UMR 7616), Universit\'e Pierre et Marie Curie, Sorbonne Universit\'e, CNRS, Paris, France} + +\begin{document} + +\title{Supporting Information for ``Chemically-Accurate Excitation Energies With Small Basis Sets''} + +\author{Emmanuel Giner} +\affiliation{\LCT} +\author{Anthony Scemama} +\affiliation{\LCPQ} +\author{Julien Toulouse} +\affiliation{\LCT} +\author{Pierre-Fran\c{c}ois Loos} +\email[Corresponding author: ]{loos@irsamc.ups-tlse.fr} +\affiliation{\LCPQ} + +\begin{abstract} +\end{abstract} + +\maketitle + +%\tableofcontents + +%%%%%%%%%%%%%%%%%%%%%%%% +\section{Geometries} +\label{sec:intro} +%%%%%%%%%%%%%%%%%%%%%%%% + +Below are given the cartesian coordinates of the compounds investigated in this study. +These are provided in Angstroms (\AA) and they have been obtained at the CC3(full)/aug-cc-pVTZ level of theory, \cite{LooSceBloGarCafJac-JCTC-18, LooBogSceCafJAc-JCTC-19} except for methylene where the FCI/TZVP geometries have been extracted from Ref.~\onlinecite{SheLeiVanSch-JCP-98}. + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Ammonia} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +\begin{verbatim} +N 0.067759 0.000000 0.000000 +H -0.313823 0.468746 -0.811891 +H -0.313823 -0.937491 0.000000 +H -0.313823 0.468746 0.811891 +\end{verbatim} + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Carbon dimer} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +\begin{verbatim} +C 0.000000 0.000000 0.624021 +C 0.000000 0.000000 -0.624021 +\end{verbatim} + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Ethylene} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +\begin{verbatim} +C 0.000000 0.666904 0.000000 +C 0.000000 -0.666904 0.000000 +H 0.000000 1.229522 0.922291 +H 0.000000 -1.229522 0.922291 +H 0.000000 1.229522 -0.922291 +H 0.000000 -1.229522 -0.922291 +\end{verbatim} + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Methylene} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +%============================== +\subsubsection{$1\,{}^3 B_1$ state} +%============================== + +\begin{verbatim} +C 0.000000 0.000000 0.000000 +H 0.000000 0.000000 1.077500 +H -0.784304 0.000000 -0.738832 +\end{verbatim} + +%============================== +\subsubsection{$1\,{}^1 A_1$ state} +%============================== + +\begin{verbatim} +C 0.000000 0.000000 0.000000 +H 0.000000 0.000000 1.108900 +H -1.085109 0.000000 -0.228470 +\end{verbatim} + +%============================== +\subsubsection{$1\,{}^1 B _1$ state} +%============================== + +\begin{verbatim} +C 0.000000 0.000000 0.000000 +H 0.000000 0.000000 1.074800 +H -0.668198 0.000000 -0.841847 +\end{verbatim} + +%============================== +\subsubsection{$2\,{}^1A_1$ state} +%============================== + +\begin{verbatim} +C 0.000000 0.000000 0.000000 +H 0.000000 0.000000 1.067800 +H -0.183953 0.000000 -1.051836 +\end{verbatim} + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Water} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +\begin{verbatim} +O 0.000000 0.000000 -0.069903 +H 0.000000 0.757532 0.518435 +H 0.000000 -0.757532 0.518435 +\end{verbatim} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\section{Total energies} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Ammonia} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Carbon dimer} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Ethylene} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + +%%%%%%%%%%%%%%%%%%%%%%%%%%% +\subsection{Water} +%%%%%%%%%%%%%%%%%%%%%%%%%%% + + +\bibliography{../Ex-srDFT,../Ex-srDFT-control} + +\end{document}