Symmetry, vibrational energy redistribution and vibronic coupling: the internal conversion processes of cycloketones
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In this paper we discern two basic mechanisms in 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 et al., ChemPhysChem 13 820 (2012)].
Original language | English |
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Journal | Journal of Chemical Physics |
Volume | 137 |
Issue number | 22 |
Number of pages | 9 |
ISSN | 0021-9606 |
DOIs | |
Publication status | Published - 2012 |
- Faculty of Science - Quantum Chemistry, Non-ergodic, intramolecular dynamics, wave packet, Multi-configuration time-dependent Hartree
Research areas
ID: 38535706