ArHF vibrational predissociation dynamics using the diatomics-in-molecule potential energy surface

A. A. Buchachenko, N. F. Stepanov, B. L. Grigorenko, A. V. Nemukhin

Research output: Contribution to journalArticlepeer-review

26 Citations (Scopus)


Vibrational predissociation dynamics of ArHF and ArDF complexes is investigated theoretically for the first time owing to the use of three-dimensional potential energy surfaces (PES's) based on the diatomics-in-molecule approach [J. Chem. Phys. 104, 5510 (1996)]. The original PES is improved empirically to yield a reasonable description of the lowest vibrational energy levels of the ArHF complex at J = 0. Predissociation dynamics is studied by means of line shape and diabatic Fermi Golden Rule methods. The latter is found to provide excellent results for the total decay widths but only a qualitative estimate for the product rotational distributions. It is shown that predissociation dynamics is governed by vibrational to rotational energy transfer. The decay proceeds almost entirely into the highest accessible rotational product channel. This propensity manifests itself in the decrease of the predissociation lifetime upon increasing vibrational excitation of the diatomic fragment when the highest rotational channel appears to be closed. Another source of state specificity in the vibrational predissociation is the anisotropy of the PES. Absolute calculated lifetime values are likely too small, but exhibit some qualitative trends observed experimentally.

Original languageEnglish
Pages (from-to)2470-2477
Number of pages8
JournalJournal of Chemical Physics
Issue number6
Publication statusPublished - 8 Aug 1999
Externally publishedYes


Dive into the research topics of 'ArHF vibrational predissociation dynamics using the diatomics-in-molecule potential energy surface'. Together they form a unique fingerprint.

Cite this