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Resonance dynamics of DCO (<(X over tilde>(2)A') simulated with the dynamically pruned discrete variable representation (DP-DVR)

  • Selected resonance states of the deuterated formyl radical in the electronic ground state X^2A´ 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 numberSelected resonance states of the deuterated formyl radical in the electronic ground state X^2A´ 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.zeige mehrzeige weniger

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Metadaten
Autoren/innen:Jens Riedel, H. Larsson, F. Temps, B. Hartke
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):THE JOURNAL OF CHEMICAL PHYSICS
Jahr der Erstveröffentlichung:2018
Organisationseinheit der BAM:P Präsidium
P Präsidium / PST Präsidiale Stabsstelle
Verlag:AIP publishing
Verlagsort:New York
Jahrgang/Band:148
Ausgabe/Heft:20
Erste Seite:204309-1
Letzte Seite:204309-15
DDC-Klassifikation:Naturwissenschaften und Mathematik / Chemie / Analytische Chemie
Freie Schlagwörter:Quantum state; Reaction dynamics; Spectroscopy
Themenfelder/Aktivitätsfelder der BAM:Analytical Sciences
Analytical Sciences / Zerstörungsfreie Prüfung und Spektroskopie
DOI:https://doi.org/10.1063/1.5026459
ISSN:0021-9606
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:03.07.2018
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:03.07.2018