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.
Highlights
Processes in excited states initiated by short laser pulses can exhibit significant non-ergodic behavior as exemplified by the cycloketones [1,2]
In this paper we present 4-state, 5-dimensional Vibronic Coupling Hamiltonians for cyclobutanone and cyclopentanone
We present in here the construction of 4-state, 5-dimensional vibronic coupling Hamiltonians (VCHAM) [3] for cyclobutanone and cyclopentanone and their use in wave packet calculations to investigate the true dynamical nature of the (n,3s) to (n,π*) transition in these molecules
Summary
Processes in excited states initiated by short laser pulses can exhibit significant non-ergodic behavior as exemplified by the cycloketones [1,2]. The direct time-scale for the (n,3s) to (n,π*) transition in these molecules exhibit such effects [2]. Contrary to the expectation of a rise in the rate of transition as ρm(E) is increased, the exact opposite trend was observed for the cycloketones [2]. This observation points to a significant coordinate dependence of the coupling matrix element in Eq 1. We present in here the construction of 4-state, 5-dimensional vibronic coupling Hamiltonians (VCHAM) [3] for cyclobutanone and cyclopentanone and their use in wave packet calculations to investigate the true dynamical nature of the (n,3s) to (n,π*) transition in these molecules
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