Quantum-dynamical modeling of the rydberg to valence excited-state internal conversion in cyclobutanone and cyclopentanone

Abstract

In this paper we present 4-state, 5-dimensional Vibronic Coupling Hamiltonians for cyclobutanone and cyclopentanone. Wave packet calculations using these Hamiltonians reveal that for cyclobutanone the (n,3s) to (n,π*) internal conversion involves direct motion in nuclear modes coupling the two states leading to fast population transfer. For cyclopentanone, internal vibrational energy redistribution is a bottleneck for activating reactive nuclear modes leading to slower population transfer. © Owned by the authors, published by EDP Sciences, 2013.