Quantum-dynamical Modeling of the Rydberg to Valence Excited-State Internal Conversion in Cyclobutanone and Cyclopentanone
1 Technical University of Denmark, Department of Chemistry, DK-2800 Kgs, Lyngby, Denmark
2 University of Copenhagen, Department of Chemistry, DK-2100, København Ø, Denmark
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
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