An efficient time-dependent golden rule treatment for three-dimensional vibrational predissociation of HeI2

Dong H. Zhang, John Zhang

Research output: Contribution to journalArticle

Abstract

Two-dimensional (2D) and three-dimensional (3D) quantum calculations for vibrational predissociation of HeI2(B) are carried out using an efficient time-dependent quantum wave packet method based on the Golden Rule approximation. The total decay widths from 2D and 3D calculations of HeI2 predissociation and their dependence on initial vibrational states are presented. Our calculations show that the total decay width from the 2D calculations is almost twice as large as from 3D calculations. It appears clear that the popular T-shaped 2D calculation, in which the rotational motion of the diatomic molecule is neglected, systematically underestimates the lifetime of the complex in agreement with earlier results of Beswick. A plausible explanation is given for why the 2D decay width is larger than the 3D decay width based on the argument of an effective centrifugal barrier. The rotational state distributions of I2 from 3D calculations are insensitive to initial vibrational state, which has also been observed in the HeCl2 system.

Original languageEnglish (US)
Pages (from-to)1575-1578
Number of pages4
JournalJournal of Physical Chemistry
Volume96
Issue number4
StatePublished - 1992

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decay
vibrational states
Wave packets
rotational states
diatomic molecules
wave packets
life (durability)
Molecules
approximation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

An efficient time-dependent golden rule treatment for three-dimensional vibrational predissociation of HeI2 . / Zhang, Dong H.; Zhang, John.

In: Journal of Physical Chemistry, Vol. 96, No. 4, 1992, p. 1575-1578.

Research output: Contribution to journalArticle

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