Efficient calculation of Franck–Condon factors and vibronic couplings in polyatomics

We present a technique for the calculation of Franck–Condon factors and other integrals between vibronic wave functions belonging to different electronic states. The technique is well suited for the determination of the nonadiabatic or spin‐orbit couplings related to radiationless decays in polyatomics. Rigorous or approximate partitions of the internal coordinate space are exploited to achieve better efficiency and/or to go beyond the harmonic approximation. The technique is tested by computing the Internal Conversion and InterSystem Crossing rates of (CH₃)₃CNO in its ¹(n→π*) state. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 968–975, 2001