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
X̃A′2 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
Open Access Journal?:	No
Publisher:	American Institute of Physics
Projects:	Future Ocean
Date Deposited:	01 Aug 2018 08:35
Last Modified:	02 Apr 2019 09:29
URI:	https://oceanrep.geomar.de/id/eprint/43878

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