Cluster perturbation theory: III. Perturbation series for coupled cluster singles and doubles excitation energies

TY - JOUR

T1 - Cluster perturbation theory

T2 - III. Perturbation series for coupled cluster singles and doubles excitation energies

AU - Baudin, Pablo

AU - Pawłowski, Filip

AU - Bykov, Dmytro

AU - Liakh, Dmitry

AU - Kristensen, Kasper

AU - Olsen, Jeppe

AU - Jørgensen, Poul

PY - 2019

Y1 - 2019

N2 - The cluster perturbation series, CPS(D), for coupled cluster singles and doubles excitation energies is considered. It is demonstrated that the second-order model CPS(D-2) is identical to the configuration interaction singles with perturbative doubles, CIS(D) model. The third-order model, CPS(D-3), provides excitation energies of coupled cluster singles and doubles (CCSD) quality in the sense that the difference between CPS(D-3) and CCSD excitation energies is of the same size or smaller than the effect of adding triples corrections to CCSD excitation energies. We further show that the third-order corrections can be efficiently implemented, in particular, when the resolution of the identity approximation is used for integrals. We also show that the CPS(D-3) excitation energies can be determined for system sizes that are far beyond what can be considered in conventional CCSD excitation energy calculations.

AB - The cluster perturbation series, CPS(D), for coupled cluster singles and doubles excitation energies is considered. It is demonstrated that the second-order model CPS(D-2) is identical to the configuration interaction singles with perturbative doubles, CIS(D) model. The third-order model, CPS(D-3), provides excitation energies of coupled cluster singles and doubles (CCSD) quality in the sense that the difference between CPS(D-3) and CCSD excitation energies is of the same size or smaller than the effect of adding triples corrections to CCSD excitation energies. We further show that the third-order corrections can be efficiently implemented, in particular, when the resolution of the identity approximation is used for integrals. We also show that the CPS(D-3) excitation energies can be determined for system sizes that are far beyond what can be considered in conventional CCSD excitation energy calculations.

KW - 3RD-ORDER

KW - BASIS-SETS

KW - CONFIGURATION-INTERACTION SINGLES

KW - ELECTRONIC-STRUCTURE

KW - EXCITED-STATES

KW - MODEL

KW - POLARIZATION PROPAGATOR

KW - RESPONSE FUNCTIONS

KW - TRANSITION-PROBABILITIES

KW - WAVE-FUNCTION

UR - http://www.scopus.com/inward/record.url?scp=85063882777&partnerID=8YFLogxK

U2 - 10.1063/1.5046935

DO - 10.1063/1.5046935

M3 - Journal article

C2 - 30954051

AN - SCOPUS:85063882777

SN - 0021-9606

VL - 150

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 13

M1 - 134110

ER -