Experimental and theoretical investigation of correlated fine structure branching ratios arising from state-selected predissociation of BrO (A2Π3/2)

Literature Information

Publication Date 2013-10-29
DOI 10.1039/C3CP53766H
Impact Factor 3.676
Authors

Michael P. Grubb, Kristin S. Dooley, C. Daniel Freeman, Kirk A. Peterson, Simon W. North


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Abstract

We present results for the v′-dependent predissociation dynamics of the BrO (A2Π3/2) state using velocity map ion imaging. Correlated fine structure branching ratios, Br(2PJ) + O(3PJ), have been measured for v′ = 5–16 states. The experimental branching ratios are non-statistical and strongly dependent on the initial vibronic state. The current measurements represent an extensive dataset containing rich information about the predissociation dynamics of this system and should provide a stringent test for modern theory. New high level ab initio excited state potentials are presented and have been optimized using experimental v′-dependent predissociation lifetimes and calculated coupling constants. Comparisons between the experimental branching ratios and the predictions based on diabatic and adiabatic limiting models are presented. We find that the adiabatic model is most consistent with the observed trends in the correlated branching ratios, in contrast to previous studies on the related ClO system.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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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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