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J Chem Phys. 2004 Aug 1;121(5):2105-16.

Excited state electronic structures and dynamics of NOCl: a new potential function set, absorption spectrum, and photodissociation mechanism.

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Department of Chemistry, Graduate School of Science, Kyoto University, 606-8502, Japan.


A set of analytical potential energy surfaces (PESs) for six singlet excited states of NOCl are constructed based on multireference configuration interaction calculations. The total absorption cross section at the energy range of 2-7 eV is calculated by quantum dynamics calculations with the present PESs and transition dipole moments. The calculated absorption spectrum agrees well with the experiment. It is also found that the A band with the absorption maximum at 6.3 eV is attributed to the transition to the 4 1A' state, though the excitations to the 3 1A' and 3 1A" states contribute to the spectrum at the energy range between 4 and 5 eV. The spin-forbidden transitions are concluded to be negligibly weak. The mechanism of photodissociation reaction at the energy region corresponding to the A band is examined. The nonadiabatic transition rates from the 4 1A' state to lower singlet and triplet states are estimated by Fermi's golden rule, and the transitions to the 1 1A' and 3 1A' states induced by vibronic coupling are found to be the predominant dissociation pathways. The experimentally observed energy dependence of the recoil anisotropy of the fragments is discussed based on the calculated nonadiabatic transition rates.

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