Self-consistent field perturbation theory of molecular vibrations

Alexei V. Sergeev, David Z. Goodson

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Perturbation theory is used to perform non-iterative calculations of energy eigenvalues of the coupled ordinary differential equations that result from imposing separability assumptions in terms of normal coordinates on vibrational wavefunctions. Various model Hamiltonians with 2 or 3 coupled normal modes are studied and the increase of computational cost with the number of degrees of freedom is analysed. Quadratic Padé approximants of the perturbation expansions are rapidly convergent, and directly yield complex numbers for resonance eigen-values. For a 3-mode system, results are obtained within partial separability assumptions, with a pair of modes left coupled. Large-order perturbation theory with partial separability is suggested as an alternative to low-order exact perturbation theory.

Original languageEnglish
Pages (from-to)477-484
Number of pages8
JournalMolecular Physics
Volume93
Issue number3
Publication statusPublished - 20 Feb 1998
Externally publishedYes

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Molecular vibrations
Hamiltonians
Wave functions
Vibration
Ordinary differential equations
self consistent fields
perturbation theory
Costs and Cost Analysis
vibration
complex numbers
Costs
coupled modes
differential equations
eigenvalues
degrees of freedom
costs
perturbation
expansion
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Sergeev, A. V., & Goodson, D. Z. (1998). Self-consistent field perturbation theory of molecular vibrations. Molecular Physics, 93(3), 477-484.

Self-consistent field perturbation theory of molecular vibrations. / Sergeev, Alexei V.; Goodson, David Z.

In: Molecular Physics, Vol. 93, No. 3, 20.02.1998, p. 477-484.

Research output: Contribution to journalArticle

Sergeev, AV & Goodson, DZ 1998, 'Self-consistent field perturbation theory of molecular vibrations', Molecular Physics, vol. 93, no. 3, pp. 477-484.
Sergeev, Alexei V. ; Goodson, David Z. / Self-consistent field perturbation theory of molecular vibrations. In: Molecular Physics. 1998 ; Vol. 93, No. 3. pp. 477-484.
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