The UV absorption of ClO - Part 2. Predissociation of the A(2)Pi(Omega) state studied by ab-initio and Fermi golden rule calculations

Ic. Lane et al., The UV absorption of ClO - Part 2. Predissociation of the A(2)Pi(Omega) state studied by ab-initio and Fermi golden rule calculations, PCCP PHYS C, 1(13), 1999, pp. 3087-3096
Citations number
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
ISSN journal
1463-9076 → ACNP
Year of publication
3087 - 3096
SICI code
Ab-initio calculations at the CASSCF and MRCI level have been performed on the valence doublet and quartet electronic states of the ClO radical in ord er to explore the predissociation dynamics of the A(2)Pi(Omega) state (Omeg a=1/2 or 3/2). The ab-initio calculations neglect spin-orbit coupling. Larg e basis sets with diffuse orbitals were employed to ensure the calculated X (2)Pi and A (2)Pi potentials match closely the available experimental data . In total, the potential energies of fifteen valence states were computed at a series of internuclear separations in order to map the potential energ y curves. The X (2)Pi, A (2)Pi and a (4)Sigma(-) potentials are bound; thou gh the latter has yet to be observed experimentally. All the other states a re repulsive, and the lowest ten cross the A (2)Pi(3/2) component at energi es below the upsilon' = 6 vibrational level. Using arguments based on elect ronic configurations, candidate states for the predissociation of the A (2) Pi(Omega) state can be selected. Simulations of the predissociation were pe rformed by Fermi golden rule calculations for each vibrational level, using the ab-initio repulsive potentials and RKR curves for the A (2)Pi(3/2) and A (2)Pi(1/2) states. The vibrational dependence of the predissociation rat e in the A (2)Pi(3/2) component was used to derive the magnitude of the ind ividual couplings with the repulsive potentials. Comparison between the lif etimes of the vibrational levels in the A (2)Pi(3/2) and A (2)Pi(1/2) compo nents restricts the principal players in the predissociation to three repul sive states: 1 (4)Sigma(Omega)(+), 2 (4)Sigma(Omega)(-) and 3 (2)Pi(Omega). The possibility of coupling between the A(2)Pi(3/2) component and the 1 (2 )Delta state is also suspected. A marked similarity is revealed for the var iation of predissociation rates with upsilon' for the A (2)Pi(3/2) and A (2 )Pi(1/2) components despite a spin-orbit state dependence of the absolute r ates for individual upsilon' levels. A repulsive 2 (2)Sigma(+) state is ide ntified which is likely to be involved in the UV photodissociation of ClO. Similar ab-initio calculations on FO have revealed no bound excited valence (2)Pi state correlating diabatically to the Cl(P-2) + O(D-1) dissociation limit.