Superior performance of Mukherjee's state-specific multi-reference coupled-cluster theory at the singles and doubles truncation scheme with localized active orbitals

Sanghamitra Das, M. Kállay, Debashis Mukherjee

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The state-specific multi-reference coupled-cluster (SS-MRCC) theory of Mukherjee et al., in its singles and doubles truncation scheme (SS-MRCCSD), misses important couplings between the virtual functions reached by single and double excitations from different model functions. Since the SS-MRCC theory is not invariant with respect to the transformations among the active orbitals, the results are dependent on the active orbitals chosen. We demonstrate in this paper with results for potential energy curves for several example molecules involving single and multiple bond dissociation that the performance of SS-MRCCSD is significantly improved if localized active orbitals are used. The improvement is remarkable both in terms of the non-parallelity error and the magnitude of correlation energy recovered vis-a-vis the full configuration interaction results with the same basis set. The results bolster our claim that SS-MRCCSD with localized orbitals is an accurate general theory for potential energy surfaces.

Original languageEnglish
Pages (from-to)83-89
Number of pages7
JournalChemical Physics
Volume392
Issue number1
DOIs
Publication statusPublished - Jan 2 2012

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orbitals
Potential energy surfaces
Potential energy
approximation
potential energy
Molecules
configuration interaction
dissociation
curves
excitation
molecules
energy

Keywords

  • Coupled-cluster
  • Localized orbitals
  • Multi-reference
  • State-specific

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

Superior performance of Mukherjee's state-specific multi-reference coupled-cluster theory at the singles and doubles truncation scheme with localized active orbitals. / Das, Sanghamitra; Kállay, M.; Mukherjee, Debashis.

In: Chemical Physics, Vol. 392, No. 1, 02.01.2012, p. 83-89.

Research output: Contribution to journalArticle

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