New scheme for solving the amplitude equations in the state-specific coupled cluster theory with complete active space reference for ground and excited states

Vladimir V. Lvanov, Ludwik Adamowicz

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

A new scheme for solving the coupled cluster (CC) amplitude equations for ground and excited electronic states in the state-selective multireference (MR) CC method based on the complete active space (CAS) reference wave function (CASCC) is proposed. The CASCC wave function is generated using a single formal reference determinant, which is one of the CAS determinants, as the origin of the configuration expansion. Some single and double excitations from other CAS determinants may be triple, quadruple, and higher excitations from the reference determinant. We show that one may include the contribution from these higher excitations indirectly by modifying the coupled cluster amplitude equations corresponding to the single and double excitations. The modification involves including projections against the higher excitations in the equations for the singles and doubles. Test calculations for the ground and the first excited state of the H8-model system and for the singlet-triplet splitting of the CH2-biradical shows that the results improve with the use of the new scheme and become to the FCI benchmarks.

Original languageEnglish (US)
Pages (from-to)8502-8513
Number of pages12
JournalThe Journal of Chemical Physics
Volume113
Issue number19
StatePublished - Nov 15 2000

Fingerprint

Wave functions
Excited states
Ground state
determinants
ground state
Electronic states
excitation
wave functions
projection
expansion
configurations
electronics

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

@article{0baafe973fa84d389041b81d5f28027e,
title = "New scheme for solving the amplitude equations in the state-specific coupled cluster theory with complete active space reference for ground and excited states",
abstract = "A new scheme for solving the coupled cluster (CC) amplitude equations for ground and excited electronic states in the state-selective multireference (MR) CC method based on the complete active space (CAS) reference wave function (CASCC) is proposed. The CASCC wave function is generated using a single formal reference determinant, which is one of the CAS determinants, as the origin of the configuration expansion. Some single and double excitations from other CAS determinants may be triple, quadruple, and higher excitations from the reference determinant. We show that one may include the contribution from these higher excitations indirectly by modifying the coupled cluster amplitude equations corresponding to the single and double excitations. The modification involves including projections against the higher excitations in the equations for the singles and doubles. Test calculations for the ground and the first excited state of the H8-model system and for the singlet-triplet splitting of the CH2-biradical shows that the results improve with the use of the new scheme and become to the FCI benchmarks.",
author = "Lvanov, {Vladimir V.} and Ludwik Adamowicz",
year = "2000",
month = "11",
day = "15",
language = "English (US)",
volume = "113",
pages = "8502--8513",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "19",

}

TY - JOUR

T1 - New scheme for solving the amplitude equations in the state-specific coupled cluster theory with complete active space reference for ground and excited states

AU - Lvanov, Vladimir V.

AU - Adamowicz, Ludwik

PY - 2000/11/15

Y1 - 2000/11/15

N2 - A new scheme for solving the coupled cluster (CC) amplitude equations for ground and excited electronic states in the state-selective multireference (MR) CC method based on the complete active space (CAS) reference wave function (CASCC) is proposed. The CASCC wave function is generated using a single formal reference determinant, which is one of the CAS determinants, as the origin of the configuration expansion. Some single and double excitations from other CAS determinants may be triple, quadruple, and higher excitations from the reference determinant. We show that one may include the contribution from these higher excitations indirectly by modifying the coupled cluster amplitude equations corresponding to the single and double excitations. The modification involves including projections against the higher excitations in the equations for the singles and doubles. Test calculations for the ground and the first excited state of the H8-model system and for the singlet-triplet splitting of the CH2-biradical shows that the results improve with the use of the new scheme and become to the FCI benchmarks.

AB - A new scheme for solving the coupled cluster (CC) amplitude equations for ground and excited electronic states in the state-selective multireference (MR) CC method based on the complete active space (CAS) reference wave function (CASCC) is proposed. The CASCC wave function is generated using a single formal reference determinant, which is one of the CAS determinants, as the origin of the configuration expansion. Some single and double excitations from other CAS determinants may be triple, quadruple, and higher excitations from the reference determinant. We show that one may include the contribution from these higher excitations indirectly by modifying the coupled cluster amplitude equations corresponding to the single and double excitations. The modification involves including projections against the higher excitations in the equations for the singles and doubles. Test calculations for the ground and the first excited state of the H8-model system and for the singlet-triplet splitting of the CH2-biradical shows that the results improve with the use of the new scheme and become to the FCI benchmarks.

UR - http://www.scopus.com/inward/record.url?scp=0034319823&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034319823&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0034319823

VL - 113

SP - 8502

EP - 8513

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 19

ER -