diff --git a/CC_cc-pvdz.txt b/CC_cc-pvdz.txt index 8ec34c3..fc958b2 100644 --- a/CC_cc-pvdz.txt +++ b/CC_cc-pvdz.txt @@ -26,7 +26,7 @@ CC3 -193.544894006853781 -0.736574222273275 CC4 -193.546686469127337 -0.738366684546823 CCSD -193.515557363805186 -0.707237579224683 CCSDT -193.544566492999309 -0.736246708418799 -CCSDTQ +CCSDTQ -193.546522140393336 -0.738202355812839 CCSD(T) -193.5438903 -0.7355705154 ===== @@ -114,7 +114,7 @@ CC3 -209.584885457786328 -0.756270764152895 CC4 -209.586191075800997 -0.757576382167585 CCSD -209.554327546276966 -0.725712852643528 CCSDT -209.583798415096226 -0.755183721462796 -CCSDTQ +CCSDTQ -209.58597559275506 -0.757360899120397 CCSD(T) -209.5835546 -0.7549399064 ========= @@ -205,7 +205,7 @@ CC3 -263.604508857029998 -0.901497912273981 CC4 -263.605647787083853 -0.902636842327822 CCSD -263.564039462108155 -0.861028517352127 CCSDT -263.602361678440957 -0.899350733684886 -CCSDTQ +CCSDTQ -263.605341720068964 -0.902330775312939 CCSD(T) -263.6024318 -0.8994208552 ========== @@ -323,7 +323,7 @@ CC3 -295.570596292645462 -0.954853218744419 CC4 -295.571623462749471 -0.955880388848436 CCSD -295.524844022789694 -0.909100948888639 CCSDT -295.567328187306430 -0.951585113405389 -CCSDTQ +CCSDTQ -295.571171239813680 -0.955428165912650 CCSD(T) -295.5679913 -0.9522482261 ======== diff --git a/Manuscript/Ec.tex b/Manuscript/Ec.tex index d479e53..ccde78a 100644 --- a/Manuscript/Ec.tex +++ b/Manuscript/Ec.tex @@ -72,7 +72,9 @@ The performance of the ground-state gold standard CCSD(T) is also investigated. \end{figure*} \section{Computational details} - +The geometries of the twelve systems considered in the present study have been all obtained at the CC3/aug-cc-pVTZ level of geometry and have been extracted from a previous study. \cite{Loos_2020a} +The MP2, MP3, MP4, CC2, CC3, CC4, CCSD, CCSDT, and CCSDTQ calculations have been performed with Cfour, \cite{cfour} while the CCSD(T) and MP5 calculations have been performed in Gaussian 09. \cite{g09} +For all these calculations, we consider Dunning's correlation-consistent double-$\zeta$ basis (cc-pVDZ) which consists of Hilbert space sizes ranging from $10^{20}$ (for thiophene) to $10^{36}$ (for benzene). We follow our usual procedure \cite{Scemama_2018,Scemama_2018b,Scemama_2019,Loos_2018a,Loos_2019,Loos_2020a,Loos_2020b,Loos_2020c} by performing a preliminary SCI calculation using Hartree-Fock orbitals in order to generate a SCI wave function with at least $10^7$ determinants. Natural orbitals are then computed based on this wave function, and a second run is performed with localized orbitals. This has the advantage to produce a smoother and faster convergence of the SCI energy toward the FCI limit by taking benefit of the local character of electron correlation.\cite{Angeli_2003,Angeli_2009,BenAmor_2011,Suaud_2017,Chien_2018,Eriksen_2020} @@ -110,7 +112,7 @@ We have found that $\expval*{\Hat{S}^2}$ is, nonetheless, very close to zero for \hline CCSD & $-193.5156$ & $-707.2$ & $-229.3783$ & $-735.0$ & $-225.5796$ & $-744.2$ & $-209.5543$ & $-725.7$ & $-552.0155$ & $-694.5$ \\ CCSDT & $-193.5446$ & $-736.2$ & $-229.4076$ & $-764.3$ & $-225.6099$ & $-774.6$ & $-209.5838$ & $-755.2$ & $-552.0461$ & $-725.1$ \\ - CCSDTQ & & & $-229.4100$ & $-766.7$ & & & & & $-552.0485$ & $-727.5$ \\ + CCSDTQ & $-193.5465$ & $-738.2$ & $-229.4100$ & $-766.7$ & & & $-209.5860$ & $-757.4$ & $-552.0485$ & $-727.5$ \\ \hline CCSD(T) & $-193.5439$ & $-735.6$ & $-229.4073$ & $-764.0$ & $-225.6099$ & $-774.5$ & $-209.5836$ & $-754.9$ & $-552.0458$ & $-724.8$ \\ @@ -144,7 +146,7 @@ We have found that $\expval*{\Hat{S}^2}$ is, nonetheless, very close to zero for \hline CCSD & $-231.5440$ & $-821.8$ & $-263.5640$ & $-861.0$ & $-263.5347$ & $-864.9$ & $-247.5559$ & $-840.7$ & $-263.5716$ & $-858.0$ & $-295.5248$ & $-909.1$ & $-279.5911$ & $-873.8$ \\ CCSDT & $-231.5802$ & $-857.9$ & $-263.6024$ & $-899.4$ & $-263.5739$ & $-904.0$ & $-247.5931$ & $-877.9$ & $-263.6097$ & $-896.1$ & $-295.5673$ & $-951.6$ & $-279.6300$ & $-912.7$ \\ - CCSDTQ & & & & & & & & & & \\ + CCSDTQ & & & $-263.6053$ & $-902.3$ & & & & & & & $-295.5712$ & $-955.4$ & & \\ \hline CCSD(T) & $-231.5798$ & $-857.5$ & $-263.6024$ & $-899.4$ & $-263.5740$ & $-904.1$ & $-247.5929$ & $-877.7$ & $-263.6099$ & $-896.2$ & $-295.5680$ & $-952.2$ & $-279.6305$ & $-913.1$ \\ \hline