diff --git a/Manuscript/H8_pes.pdf b/Manuscript/H8_pes.pdf index 0a86520..89e1dda 100644 Binary files a/Manuscript/H8_pes.pdf and b/Manuscript/H8_pes.pdf differ diff --git a/Manuscript/H8_pes_error.pdf b/Manuscript/H8_pes_error.pdf index f331c10..460b341 100644 Binary files a/Manuscript/H8_pes_error.pdf and b/Manuscript/H8_pes_error.pdf differ diff --git a/Manuscript/sup.tex b/Manuscript/sup.tex index 6399f2f..bd9f66f 100644 --- a/Manuscript/sup.tex +++ b/Manuscript/sup.tex @@ -70,20 +70,6 @@ % Title \maketitle -%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -%\section{\ce{Computational details}} -%\label{sec:comp_details} -%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% - -Vibrational frequencies and equilibrium geometries were obtained by fitting the computed potential energy curves limited to the Franck-Condon region with a Morse potential. -The following intervals have been considered for the fitting: -\SI{0.8}{\angstrom} to \SI{1.3}{\angstrom} (\ce{HF}), -\SI{1.25}{\angstrom} to \SI{1.65}{\angstrom} (\ce{F2}), -\SI{2.2}{\bohr} to \SI{2.9}{\bohr} (ethylene), -\SI{0.95}{\angstrom} to \SI{1.3}{\angstrom} (\ce{N2}), -\SI{1.45}{\bohr} to \SI{1.95}{\bohr} (\ce{H4}), -\SI{1.6}{\bohr} to \SI{2.05}{\bohr} (\ce{H8}). - %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% %\section{Equilibrium geometry of ethylene} %\label{sec:ethylene} @@ -100,6 +86,58 @@ Equilibrium geometry of ethylene, in atomic units. H & 0.00000000 & -2.32345976 & -1.74287672 \\ \end{tabular} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%\section{\ce{Computational details}} +%\label{sec:comp_details} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% + +Vibrational frequencies and equilibrium geometries were obtained by fitting the computed potential energy curves at the Franck-Condon region with a Morse potential. +The following intervals have been considered for the fitting: +\SI{0.8}{\angstrom} to \SI{1.3}{\angstrom} (\ce{HF}), +\SI{1.25}{\angstrom} to \SI{1.65}{\angstrom} (\ce{F2}), +\SI{2.2}{\bohr} to \SI{2.9}{\bohr} (ethylene), +\SI{0.95}{\angstrom} to \SI{1.3}{\angstrom} (\ce{N2}), +\SI{1.45}{\bohr} to \SI{1.95}{\bohr} (\ce{H4}), +\SI{1.6}{\bohr} to \SI{2.05}{\bohr} (\ce{H8}). + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%\section{\ce{HF}, different basis sets} +%\label{sec:HF_basis} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% + +\begin{figure}[h!] +\includegraphics[width=\linewidth]{plot_pes_HF} + \caption{Potential energy curves (top) and energy differences with respect to FCI (bottom), for dissociation of \ce{HF}, + according to the three classes of CI methods: seniority-based CI (blue), excitation-based CI (red), and hierarchy-based CI (green), + with Hartree-Fock orbitals, + and for the cc-pVDZ (left), cc-pVTZ (center), and cc-pVQZ (right) basis sets. + } + \label{fig:plot_pes_HF} +\end{figure} + +\begin{figure}[h!] +\includegraphics[width=\linewidth]{freq_HF} + \caption{Non-parallelity error (left), vibrational frequencies (center), and equilibrium geometries (right) of \ce{HF}, + as function of the number of determinants, + according to the three classes of CI methods: seniority-based CI (blue), excitation-based CI (red), and hierarchy-based CI (green), + with Hartree-Fock orbitals, + and for the cc-pVDZ (left), cc-pVTZ (center), and cc-pVQZ (right) basis sets.} + \label{fig:freq_HF} +\end{figure} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%\section{Distance error} +%\label{sec:distance} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% + +\begin{figure}[h!] +\includegraphics[width=0.8\linewidth]{plot_distance} + \caption{Distance errors as function of the number of determinants, for the three classes of CI methods: seniority-based CI (blue), excitation-based CI (red), and hierarchy-based CI (green), + with Hartree-Fock orbitals. + } + \label{fig:plot_distance} +\end{figure} + %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% %\section{oo-CI} %\label{sec:oo-CI} @@ -149,31 +187,6 @@ Equilibrium geometry of ethylene, in atomic units. \label{fig:plot_pes} \end{figure} -%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -%\section{\ce{HF}, different basis sets} -%\label{sec:HF_basis} -%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% - -\begin{figure}[h!] -\includegraphics[width=\linewidth]{plot_pes_HF} - \caption{Potential energy curves (top) and energy differences with respect to FCI (bottom), for dissociation of \ce{HF}, - according to the three classes of CI methods: seniority-based CI (blue), excitation-based CI (red), and hierarchy-based CI (green), - with Hartree-Fock orbitals, - and for the cc-pVDZ (left), cc-pVTZ (center), and cc-pVQZ (right) basis sets. - } - \label{fig:plot_pes_HF} -\end{figure} - -\begin{figure}[h!] -\includegraphics[width=\linewidth]{freq_HF} - \caption{Non-parallelity error (left), vibrational frequencies (center), and equilibrium geometries (right) of \ce{HF}, - as function of the number of determinants, - according to the three classes of CI methods: seniority-based CI (blue), excitation-based CI (red), and hierarchy-based CI (green), - with Hartree-Fock orbitals, - and for the cc-pVDZ (left), cc-pVTZ (center), and cc-pVQZ (right) basis sets.} - \label{fig:freq_HF} -\end{figure} - %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% %\section{\ce{HF}} %\label{sec:HF}