Modified Born-Oppenheimer basis for nonadiabatic coupling: Application to the vibronic spectrum of HD

Inbal Tuvi, Y. B. Band

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Nonadiabatic matrix elements, when computed using a Born-Oppenheimer (BO) basis, do not vanish asymptotically because the motion of the electrons with the nuclei at large internuclear separations is not taken into account. We apply a method suggested by Delos [Rev. Mod. Phys. 53, 287 (1981)] to include the effect of electron translation factors in a quantum-mechanical framework, thus correcting the BO basis to incorporate proper boundary conditions. We calculate the nonadiabatic matrix elements for H+2 and its isotopic variants. We focus our calculations on HD+, for which experimental results exist, and calculate its vibronic spectrum. This is the first application of this method to calculate high precision spectroscopic information for molecular systems.

Original languageEnglish
Pages (from-to)5808-5823
Number of pages16
JournalJournal of Chemical Physics
Volume111
Issue number13
DOIs
StatePublished - 1 Oct 1999

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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