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

摘要: Multireference spin-orbit configuration interaction calculations of transition moments from the X A1 ground state to 3Q0+, 3Q1, and 1Q excited states responsible for A absorption band CH3I are reported employed an analysis photofragmentation in this system. Contrary what is usually assumed, 3Q0+(A1), 3Q1(E), 1Q(E) 0.9) may be achieved when vibrationally hot molecules appropriate spectral range. It shown that vibrational control I*/I branching ratio alkyl (hydrogen) iodide photodissociation has electronic rather than a dynamic nature: Due different electron density distribution at various molecular geometries, one achieves more efficient excitation particular fragmentation channel influences dynamics decay process.