Correlated fine structure branching ratios arising from state-selected predissociation of ClO (A2Π3/2)

文献情報

出版日 2009-04-29

DOI 10.1039/B823004H

インパクトファクター 3.676

著者

Kristin S. Dooley, Michael P. Grubb, Justine Geidosch, Marloes A. van Beek, Gerrit C. Groenenboom, Simon W. North

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要旨

We have extended our investigation of the v′-dependent predissociation dynamics of the ClO A2Π3/2 state using velocity-map ion imaging. Correlated fine-structure branching ratios are reported for v′ = 0–5. The measured branching ratios are non-statistical and are qualitatively inconsistent with adiabatic dissociation dynamics. The coupling constants between the A2Π3/2 state and several dissociative excited state potentials have been optimized, as have the locations of the crossing points, based on comparison to previously reported v′-dependent predissociation rates. Using these optimized potentials we have modeled the branching ratios in the diabatic limit but the lack of agreement with experiments suggests the importance of exit channel coupling. Coupled channel calculations including 9 coupled potentials provide modest improvement with experiment but differences remain.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 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.

Correlated fine structure branching ratios arising from state-selected predissociation of ClO (A2Π3/2)

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