Photodissociation of vibrationally excited water in the first absorption band

摘要

We investigate the photodissociation of highly excited vibrational states of water in the first absorption band. The calculation includes anabinitiopotential energy surface for theAtilde;hyphen;state and anabinitioXtilde;rarr;Atilde; transition dipole function. The bending angle is fixed at the equilibrium value within the ground electronic state. Most interesting is the high sensitivity of the final vibrational distribution of OH on the initially prepared vibrational state of H2O. At wavelengths near the onset of the absorption spectrum the vibrational state distribution can be qualitatively understood as a Franckndash;Condon mapping of the initial H2O wave function. At smaller wavelengths final state interaction in the excited state becomes stronger and the distributions become successively broader. Our calculations are in satisfactory accord with recent measurements of Vander Wal and Crim.