An ab initio study of the CH3I photodissociation.: II.: Transition moments and vibrational state control of the I* quantum yields

Multireference spin-orbit configuration interaction calculations of transition moments from the X A(1) ground state to the 3Q(0)(+), (3)Q(1), and (1)Q excited states responsible for the A absorption band of CH3I are reported and employed for an analysis of the photofragmentation in this system. Contrary to what is usually assumed, the (3)Q(0)(+)(A(1)), (3)Q(1)(E), and (1)Q(E)<- X A(1) transition moments are found to be strongly dependent on the C-I fragmentation coordinate. The sign of this dependence is opposite for the parallel and perpendicular transitions, which opens an opportunity for vibrational state control of the photodissociation product yields. The computed absorption intensity distribution and the I-* quantum yield as a function of excitation energy are analyzed in comparison with existing experimental data, and good agreement between theory and experiment is found. It is predicted that significantly higher I-* quantum yield values (>0.9) may be achieved when vibrationally hot CH3I molecules are excited in the appropriate spectral range. It is shown that vibrational state control of the I-*/I branching ratio in the alkyl (hydrogen) iodide photodissociation has an electronic rather than a dynamic nature: Due to a different electron density distribution at various molecular geometries, one achieves a more efficient excitation of a particular fragmentation channel rather than influences the dynamics of the decay process. (c) 2007 American Institute of Physics.