Resonance dynamics of DCO (X̃ A′2) simulated with the dynamically pruned discrete variable representation (DP-DVR)

Larsson, Henrik R., Riedel, Jens, Wei, Jie, Temps, Friedrich and Hartke, Bernd (2018) Resonance dynamics of DCO (X̃ A′2) simulated with the dynamically pruned discrete variable representation (DP-DVR) The Journal of Chemical Physics, 148 (20). p. 204309. DOI 10.1063/1.5026459.

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Abstract

Selected resonance states of the deuterated formyl radical in the electronic ground state X̃^2 A′ are computed using our recently introduced dynamically pruned discrete variable representation [H. R. Larsson, B. Hartke, and D. J. Tannor, J. Chem. Phys. 145, 204108 (2016)]. Their decay and asymptotic distributions are analyzed and, for selected resonances, compared to experimental results obtained by a combination of stimulated emission pumping and velocity-map imaging of the product D atoms. The theoretical results show good agreement with the experimental kinetic energy distributions. The intramolecular vibrational energy redistribution is analyzed and compared with previous results from an effective polyad Hamiltonian. Specifically, we analyzed the part of the wavefunction that remains in the interaction region during the decay. The results from the polyad Hamiltonian could mainly be confirmed. The C=O stretch quantum number is typically conserved, while the D—C=O bend quantum number decreases. Differences are due to strong anharmonic coupling such that all resonances have major contributions from several zero-order states. For some of the resonances, the coupling is so strong that no further zero-order states appear during the dynamics in the interaction region, even after propagating for 300 ps.

Document Type: Article
Research affiliation: Kiel University > Kiel Marine Science
OceanRep > The Future Ocean - Cluster of Excellence
Kiel University
Refereed: Yes
DOI etc.: 10.1063/1.5026459
ISSN: 0021-9606
Date Deposited: 07 Aug 2019 12:50
Last Modified: 02 Jan 2020 12:22
URI: http://eprints.uni-kiel.de/id/eprint/47423

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