Signatures of non-adiabatic dynamics in the fine-structure state distributions of the OH(X{sup ~}/A{sup ~}) products in the B-band photodissociation of H{sub 2}O
- Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China)
- Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
A detailed quantum mechanical characterization of the photodissociation dynamics of H{sub 2}O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X{sup ~}/A{sup ~}) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X{sup ~}, v = 0) exhibit very different characteristics. The A′ states, produced mostly via the B{sup ~}→X{sup ~} conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B{sup ~}→A{sup ~} Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X{sup ~}) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B{sup ~}→X{sup ~} non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(A{sup ~}) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.
- OSTI ID:
- 22415572
- Journal Information:
- Journal of Chemical Physics, Vol. 142, Issue 12; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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