Unitary perturbation theory applied to multiconfigurational reference functions

Péter R. Nagy, A. Szabados

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Unitary parametrization of the wave operator in the form suggested by Mayer is studied in the multireference framework. The investigated unitary perturbation theory (UPT) constructs a first correction in terms of the functions having nonzero interaction with the reference state via the Hamiltonian. Parameters in the exponential of the wave operator are determined by two dimensional eigenvalue equations. Because of the unitary mapping, UPT is unaffected by the quasi-degeneracy problem, making it an ideal tool for correcting multireference starting functions. Lack of size-consistency is however a shortcoming of the method. Applications of UPT as well as the related degeneracy-corrected PT (DCPT) are presented on intruder prone examples like the symmetric dissociation of the water molecule, the BeH2 system and the two lowest lying states of the scandium dimer. Size consistency violation is analysed and evaluated on the example of the water dimer. Tractability of excited states by UPT is examined by computing the singlet-triplet splitting of the CH2 molecule.

Original languageEnglish
Pages (from-to)230-238
Number of pages9
JournalInternational Journal of Quantum Chemistry
Volume113
Issue number3
DOIs
Publication statusPublished - Feb 5 2013

Fingerprint

Dimers
perturbation theory
Scandium
Hamiltonians
Molecules
Water
Excited states
Mathematical operators
dimers
operators
scandium
water
molecules
eigenvalues
dissociation
excitation
interactions

Keywords

  • intruder state problem
  • Jacobi rotation
  • multireference function
  • perturbation theory
  • unitary wave operator

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Cite this

Unitary perturbation theory applied to multiconfigurational reference functions. / Nagy, Péter R.; Szabados, A.

In: International Journal of Quantum Chemistry, Vol. 113, No. 3, 05.02.2013, p. 230-238.

Research output: Contribution to journalArticle

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