Symmetry, vibrational energy redistribution and vibronic coupling: the internal conversion processes of cycloketones

TY - JOUR

T1 - Symmetry, vibrational energy redistribution and vibronic coupling

T2 - the internal conversion processes of cycloketones

AU - Kuhlman, Thomas Scheby

AU - Sauer, Stephan P. A.

AU - Sølling, Theis Ivan

AU - Møller, Klaus Braagaard

N1 - 22A522

PY - 2012/12/14

Y1 - 2012/12/14

N2 - In this paper, we discern two basic mechanisms of internal conversion processes; one direct, where immediate activation of coupling modes leads to fast population transfer and one indirect, where internal vibrational energy redistribution leads to equidistribution of energy, i.e., ergodicity, and slower population transfer follows. Using model vibronic coupling Hamiltonians parameterized on the basis of coupled-cluster calculations, we investigate the nature of the Rydberg to valence excited-state internal conversion in two cycloketones, cyclobutanone and cyclopentanone. The two basic mechanisms can amply explain the significantly different time scales for this process in the two molecules, a difference which has also been reported in recent experimental findings [T. S. Kuhlman, T. I. Solling, and K. B. Moller, ChemPhysChem. 13, 820 (2012)]10.1002/cphc.201100929.

AB - In this paper, we discern two basic mechanisms of internal conversion processes; one direct, where immediate activation of coupling modes leads to fast population transfer and one indirect, where internal vibrational energy redistribution leads to equidistribution of energy, i.e., ergodicity, and slower population transfer follows. Using model vibronic coupling Hamiltonians parameterized on the basis of coupled-cluster calculations, we investigate the nature of the Rydberg to valence excited-state internal conversion in two cycloketones, cyclobutanone and cyclopentanone. The two basic mechanisms can amply explain the significantly different time scales for this process in the two molecules, a difference which has also been reported in recent experimental findings [T. S. Kuhlman, T. I. Solling, and K. B. Moller, ChemPhysChem. 13, 820 (2012)]10.1002/cphc.201100929.

KW - Faculty of Science

KW - Quantum Chemistry

KW - Non-ergodic

KW - intramolecular dynamics

KW - wave packet

KW - Multi-configuration time-dependent Hartree

U2 - 10.1063/1.4742313

DO - 10.1063/1.4742313

M3 - Journal article

C2 - 23249059

SN - 0021-9606

VL - 137

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

IS - 22

ER -