Three-dimensional photodissociation dynamics of rotational state selected methyl iodide

Daiqian Xie, Hua Guo*, Yoshiaki Amatatsu, Ronnie Kosloff

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

65 Scopus citations

Abstract

We report three-dimensional quantum mechanical calculations on the photodissociation dynamics of CH3I and CD3I on new ab initio potential energy surfaces. The improved potentials are obtained in the contracted spin - orbit configuration interaction framework by using a larger basis set and more spin-free configurations. The dynamical model includes the C-I stretch, C-H3 umbrella bend, and I-C-H3 bend and allows the overall rotation. The wave packet is propagated in the Chebyshev order domain. The absorption spectrum, product vibrational and rotational distributions, I* quantum yield, and state-resolved angular distributions are calculated for the parent states of |JMK〉 -|000〉 and |111〉, and compared with experiments. The new potential energy surfaces yield a much better agreement with the experimental absorption spectrum, thanks to small potential gradients in the Franck-Condon region. The calculated rovibrational distributions of the methyl fragment are also in good agreement with experimental data. It is shown that the overall rotation has significant effects on the methyl rotational and vibrational distributions as well as the I* yield.

Original languageEnglish
Pages (from-to)1009-1019
Number of pages11
JournalJournal of Physical Chemistry A
Volume104
Issue number5
DOIs
StatePublished - 10 Feb 2000

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