Basis set convergence of high-order coupled cluster methods up to CCSDTQ567 for a highly multireference molecule

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Abstract

We examine the basis-set convergence of post-CCSD(T) contributions to the dissociation energy of the highly multireference C2(1Σg +) molecule. At the infinite basis set limit we obtain: CCSDT–CCSD(T)/cc-pV{6,7}Z = −2.268, CCSDT(Q)–CCSDT/cc-pV{6,7}Z = 3.420, CCSDTQ–CCSDT(Q)/cc-pV{5,6}Z = −1.151, CCSDTQ(5)–CCSDTQ/cc-pV{Q,5}Z = 0.412, CCSDTQ5–CCSDTQ(5)/cc-pV{T,Q}Z = −0.053, CCSDTQ5(6)–CCSDTQ5/cc-pV{D,T}Z = 0.060, CCSDTQ56–CCSDTQ5(6)/cc-pVTZ(1d) = 0.003, CCSDTQ56(7)–CCSDTQ56/cc-pVTZ(1d) = 0.002, and CCSDTQ567–CCSDTQ56(7)/cc-pVTZ(1d) = 0.001 kcal/mol. These post-CCSD(T) contributions add to 0.427 kcal/mol. Including the CCSD(T)/CBS energy, inner-shell, scalar relativistic, spin-orbit, DBOC, and ZPVE corrections from W4.3 theory results in a CCSDTQ567/CBS D0 value of 144.08 kcal/mol, which agrees to within overlapping uncertainties with the experimental ATcT value of 144.006 ± 0.06 kcal/mol.

Original languageEnglish
Article number136810
JournalChemical Physics Letters
Volume737
DOIs
Publication statusPublished - 16 Dec 2019

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Orbits
Molecules
molecules
dissociation
scalars
orbits
energy
Uncertainty

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@article{bdcb0975ae8845e09f39b4a37ac99cf8,
title = "Basis set convergence of high-order coupled cluster methods up to CCSDTQ567 for a highly multireference molecule",
abstract = "We examine the basis-set convergence of post-CCSD(T) contributions to the dissociation energy of the highly multireference C2(1Σg +) molecule. At the infinite basis set limit we obtain: CCSDT–CCSD(T)/cc-pV{6,7}Z = −2.268, CCSDT(Q)–CCSDT/cc-pV{6,7}Z = 3.420, CCSDTQ–CCSDT(Q)/cc-pV{5,6}Z = −1.151, CCSDTQ(5)–CCSDTQ/cc-pV{Q,5}Z = 0.412, CCSDTQ5–CCSDTQ(5)/cc-pV{T,Q}Z = −0.053, CCSDTQ5(6)–CCSDTQ5/cc-pV{D,T}Z = 0.060, CCSDTQ56–CCSDTQ5(6)/cc-pVTZ(1d) = 0.003, CCSDTQ56(7)–CCSDTQ56/cc-pVTZ(1d) = 0.002, and CCSDTQ567–CCSDTQ56(7)/cc-pVTZ(1d) = 0.001 kcal/mol. These post-CCSD(T) contributions add to 0.427 kcal/mol. Including the CCSD(T)/CBS energy, inner-shell, scalar relativistic, spin-orbit, DBOC, and ZPVE corrections from W4.3 theory results in a CCSDTQ567/CBS D0 value of 144.08 kcal/mol, which agrees to within overlapping uncertainties with the experimental ATcT value of 144.006 ± 0.06 kcal/mol.",
keywords = "Basis set extrapolations, Basis set limit, CCSDT, CCSDTQ, CCSDTQ5, CCSDTQ56",
author = "Amir Karton",
year = "2019",
month = "12",
day = "16",
doi = "10.1016/j.cplett.2019.136810",
language = "English",
volume = "737",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Pergamon",

}

TY - JOUR

T1 - Basis set convergence of high-order coupled cluster methods up to CCSDTQ567 for a highly multireference molecule

AU - Karton, Amir

PY - 2019/12/16

Y1 - 2019/12/16

N2 - We examine the basis-set convergence of post-CCSD(T) contributions to the dissociation energy of the highly multireference C2(1Σg +) molecule. At the infinite basis set limit we obtain: CCSDT–CCSD(T)/cc-pV{6,7}Z = −2.268, CCSDT(Q)–CCSDT/cc-pV{6,7}Z = 3.420, CCSDTQ–CCSDT(Q)/cc-pV{5,6}Z = −1.151, CCSDTQ(5)–CCSDTQ/cc-pV{Q,5}Z = 0.412, CCSDTQ5–CCSDTQ(5)/cc-pV{T,Q}Z = −0.053, CCSDTQ5(6)–CCSDTQ5/cc-pV{D,T}Z = 0.060, CCSDTQ56–CCSDTQ5(6)/cc-pVTZ(1d) = 0.003, CCSDTQ56(7)–CCSDTQ56/cc-pVTZ(1d) = 0.002, and CCSDTQ567–CCSDTQ56(7)/cc-pVTZ(1d) = 0.001 kcal/mol. These post-CCSD(T) contributions add to 0.427 kcal/mol. Including the CCSD(T)/CBS energy, inner-shell, scalar relativistic, spin-orbit, DBOC, and ZPVE corrections from W4.3 theory results in a CCSDTQ567/CBS D0 value of 144.08 kcal/mol, which agrees to within overlapping uncertainties with the experimental ATcT value of 144.006 ± 0.06 kcal/mol.

AB - We examine the basis-set convergence of post-CCSD(T) contributions to the dissociation energy of the highly multireference C2(1Σg +) molecule. At the infinite basis set limit we obtain: CCSDT–CCSD(T)/cc-pV{6,7}Z = −2.268, CCSDT(Q)–CCSDT/cc-pV{6,7}Z = 3.420, CCSDTQ–CCSDT(Q)/cc-pV{5,6}Z = −1.151, CCSDTQ(5)–CCSDTQ/cc-pV{Q,5}Z = 0.412, CCSDTQ5–CCSDTQ(5)/cc-pV{T,Q}Z = −0.053, CCSDTQ5(6)–CCSDTQ5/cc-pV{D,T}Z = 0.060, CCSDTQ56–CCSDTQ5(6)/cc-pVTZ(1d) = 0.003, CCSDTQ56(7)–CCSDTQ56/cc-pVTZ(1d) = 0.002, and CCSDTQ567–CCSDTQ56(7)/cc-pVTZ(1d) = 0.001 kcal/mol. These post-CCSD(T) contributions add to 0.427 kcal/mol. Including the CCSD(T)/CBS energy, inner-shell, scalar relativistic, spin-orbit, DBOC, and ZPVE corrections from W4.3 theory results in a CCSDTQ567/CBS D0 value of 144.08 kcal/mol, which agrees to within overlapping uncertainties with the experimental ATcT value of 144.006 ± 0.06 kcal/mol.

KW - Basis set extrapolations

KW - Basis set limit

KW - CCSDT

KW - CCSDTQ

KW - CCSDTQ5

KW - CCSDTQ56

UR - http://www.scopus.com/inward/record.url?scp=85073029472&partnerID=8YFLogxK

U2 - 10.1016/j.cplett.2019.136810

DO - 10.1016/j.cplett.2019.136810

M3 - Article

VL - 737

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

M1 - 136810

ER -