dorsal/arxiv
View SchemaIntermolecular vibrational energy redistribution in DCO (X^2A'): Classical-Quantum correspondence, dynamical assignments of highly excited states, and phase space transport
| Authors | A. Semparithi, S. Keshavamurthy |
|---|---|
| Categories | |
| ArXiv ID | physics/0307129 |
| URL | https://arxiv.org/abs/physics/0307129 |
| DOI | 10.1039/B308813H |
Abstract
Intermolecular dynamics of highly excited DCO (X^2A') is studied from a classical-quantum perspective using the effective spectroscopic Hamiltonian proposed recently by Trollch and Temps (Z. Phy. Chem. 215, 207 (2001)). This work focuses on the polyads P = 3 and P = 4 corresponding to excitation energies E_v ~ 5100 cm^-1 and 7000 cm^-1 respectively. The majority of states belonging to these polyads are dynamically assigned, despite extensive stochasticity in the classical phase space, using the recently proposed technique of level velocities. A wavelet based time-frequency analysis is used to reveal the nature of phase space transport and the relevant dynamical bottlenecks. The local frequency analysis clearly illustrates the existence of mode-specific IVR dynamics i.e., differing nature of the IVR dynamics ensuing from CO stretch and the DCO bend bright states. In addition the role of the weak Fermi resonance involving the CO stretch and DCO bend modes is investigated. A key feature of the present work is that the techniques utilized for the analysis i.e., parametric variations and local frequency analysis are not limited by the dimensionality of the system. This study, thus, explores the potential for understanding IVR in large molecules from both time domain and frequency domain perspectives.
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"abstract": "Intermolecular dynamics of highly excited DCO (X^2A\u0027) is studied from a\nclassical-quantum perspective using the effective spectroscopic Hamiltonian\nproposed recently by Trollch and Temps (Z. Phy. Chem. 215, 207 (2001)). This\nwork focuses on the polyads P = 3 and P = 4 corresponding to excitation\nenergies E_v ~ 5100 cm^-1 and 7000 cm^-1 respectively. The majority of states\nbelonging to these polyads are dynamically assigned, despite extensive\nstochasticity in the classical phase space, using the recently proposed\ntechnique of level velocities. A wavelet based time-frequency analysis is used\nto reveal the nature of phase space transport and the relevant dynamical\nbottlenecks. The local frequency analysis clearly illustrates the existence of\nmode-specific IVR dynamics i.e., differing nature of the IVR dynamics ensuing\nfrom CO stretch and the DCO bend bright states. In addition the role of the\nweak Fermi resonance involving the CO stretch and DCO bend modes is\ninvestigated. A key feature of the present work is that the techniques utilized\nfor the analysis i.e., parametric variations and local frequency analysis are\nnot limited by the dimensionality of the system. This study, thus, explores the\npotential for understanding IVR in large molecules from both time domain and\nfrequency domain perspectives.",
"arxiv_id": "physics/0307129",
"authors": [
"A. Semparithi",
"S. Keshavamurthy"
],
"categories": [
"physics.chem-ph"
],
"doi": "10.1039/B308813H",
"title": "Intermolecular vibrational energy redistribution in DCO (X^2A\u0027): Classical-Quantum correspondence, dynamical assignments of highly excited states, and phase space transport",
"url": "https://arxiv.org/abs/physics/0307129"
},
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