Multiresolution potential energy surfaces for vibrational state calculations

Kiyoshi Yagi, So Hirata, Kimihiko Hirao

Research output: Contribution to journalArticlepeer-review

Abstract

A compact and robust many-mode expansion of potential energy surfaces (PES) is presented for anharmonic vibrations of polyatomic molecules, where the individual many-mode terms are approximated with various different resolutions, i.e., electronic structure methods, basis sets, and functional forms. As functional forms, the following three representations have been explored: numerical values on a grid, cubic spline interpolation, and a Taylor expansion. A useful index is proposed which rapidly identifies important many-mode terms that warrant a high resolution. Applications to water and formaldehyde demonstrate that the present scheme can increase the efficiency of the PES computation by a factor of up to 11 with the errors in anharmonic vibrational frequencies being no worse than ~ 10cm-1.

Original languageEnglish (US)
Pages (from-to)681-691
Number of pages11
JournalTheoretical Chemistry Accounts
Volume118
Issue number3
DOIs
StatePublished - Sep 1 2007
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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