Classical, quantum and statistical simulations of vibrationally excited HOSO2: IVR, dissociation, and implications for OH + SO2 kinetics at high pressures

Literature Information

Publication Date 2008-12-11
DOI 10.1039/B816108A
Impact Factor 3.676
Authors

David R. Glowacki, Stewart K. Reed, Michael J. Pilling, Dmitrii V. Shalashilin


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Abstract

In this paper, we present classical and coupled coherent states quantum dynamics simulations to investigate intramolecular vibrational energy redistribution (IVR) from an excited (v = 1–10) OH stretch within the HOSO2 complex to the other molecular bath modes. Using an analytical PES derived from electronic structure theory calculations, the results obtained from both the classical and quantum simulations are in reasonable agreement. The dynamics results suggest that statistical models overpredict HOSO2 dissociation k(E)s, and underpredict the amount of vibrational excitation in the nascent OH formed following complex dissociation. In order to understand the dynamics results, we utilize a simple analytical model for describing energy flow from excited modes to bath modes, and show that IVR limits complex dissociation at short times. We also consider qualitative mass affects on IVR, and consider the implications of this work on previous measurements of the OH + SO2 association k∞ using the proxy method.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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