ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We present results of full-dimensional quasiclassical trajectory calculations of the photodissociation of H2O(3νOH,X˜–A˜) and Ar–H2O(3νOH,X˜–A˜) at 243 and 218 nm, and compare the resulting OH rotational distributions, and also relate them to recent experiments of Nesbitt and co-workers [D. F. Plusquellic, O. Votava, and D. J. Nesbitt, J. Chem. Phys. 101, 6356 (1994)]. The dynamics calculations make use of a new six degree-of-freedom potential for Ar–H2O(A˜), which is reported here. The potential is based on a previously reported ab initio H2O A˜-state potential, a semiempirical Ar–OH(2Π) potential, and a semiempirical Ar–H potential, together with an appropriate switching function to ensure permutation symmetry with respect to the two H atoms. Initial conditions for the trajectories are obtained from a product of a Husimi phase-space density for the Ar–H2O(X˜) intermolecular modes and a Wigner/classical phase-space density for the H2O(X˜) intramolecular modes. The Husimi phase-space density is derived from the ground-state wave function for Ar–H2O(X˜), using a previous spectroscopically empirical potential. To assess the accuracy of the trajectory approach, trajectory calculations are also reported for X˜–A˜ photodissociation of H2O in the ground vibrational state at 166 nm and compared with the corresponding full-dimensional quantum wave packet calculations of von Dirke and Schinke. To further assess the accuracy of the A˜-state potential surface for H2O, calculations for H2O(4νOH,X˜–A˜) are also reported at 218 nm and compared with experiment. Rotation/vibration distributions of the OH fragment are also calculated for photodissociation of Ar–H2O(4νOH,X˜–A˜) at 218 nm. © 1996 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.471586
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