THE PHOTOABSORPTION SPECTRUM OF NA-CENTER-DOT-CENTER-DOT-CENTER-DOT-FH VAN-DER-WAALS MOLECULE - COMPARISON OF THEORY AND EXPERIMENT FOR A HARPOONING REACTION STUDIED BY TRANSITION-STATE SPECTROSCOPY

The photodissociation of Na ... FH van der Waals molecules in the 1.5- 2.3 eV energy region is a very interesting system for transition state spectroscopy, because the potential energy surfaces for electronicall y excited states funnel the system down to the ground electronic state in a critical region where detailed features of the potential energy surfaces may be important in determining the branching probability bet ween the harpooning reaction to form NaF or the dissociative E-->V ene rgy transfer process to form vibrationally excited HF. We used an anal ytic representation. reported earlier, of the potential surfaces for t he two lowest A' electronic states of NaFa I as well as separable fits for two higher excited potential surfaces to simulate the experimenta l photodepletion spectrum of the Na FI-I van der Waals molecule. Franc k-Condon analysis was performed for the (X) over tilde (2)A' --> (2)A' , (X) over tilde (2)A' --> (B) over tilde (2)A '', and (X) over tilde (2)A' --> (B) over tilde' (2)A' transitions to predissociative states of the exciplex by making a separable approximation in Jacobi coordina tes. Theoretical simulation based on ab initio energies and transition dipole moments produced an excitation spectrum that is in good agreem ent with the experimental data. Including the dependence of the transi tion dipole moment on nuclear geometry had only a small quantitative e ffect on the calculated photoabsorption spectrum. The present calculat ion, in spite of the approximations involved, provides a semiquantitat ive description of the experimental spectrum of the resonance states i n the funnel and allows us to explain all the main features of the spe ctrum. (C) 1998 American Institute of Physics. [S0021-9606(98)00913-1] .