Symmetry, vibrational energy redistribution and vibronic coupling: The internal conversion processes of cycloketones
- Authors:
- Subtitle:
- the internal conversion processes of cycloketones
- DOI:
- 10.1063/1.4742313
- Abstract:
- 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. Sølling, and K. B. Møller, ChemPhysChem. 13, 820 (2012)]
- Type:
- Journal article
- Language:
- English
- Published in:
- Journal of Chemical Physics, 2012, Vol 137, Issue 22
- Keywords:
- The Faculty of Science; Quantum Chemistry; Non-ergodic; intramolecular dynamics; wave packet; Multi-configuration time-dependent Hartree
- Main Research Area:
- Science/technology
- Publication Status:
- Published
- Review type:
- Peer Review
- Submission year:
- 2012
- Scientific Level:
- Scientific
- ID:
- 234385404
0000-0002-9797-7437
