Predissociation dynamics in the A 3Π state of PH: An experimental and ab initio investigation

Literature Information

Publication Date 2002-02-27
DOI 10.1039/B111198C
Impact Factor 3.676
Authors

James A. J. Fitzpatrick, Oleg V. Chekhlov, David R. Morgan, Robert W. Burrows, Colin M. Western


View Original

Abstract

An investigation into the predissociation dynamics of the A 3Π state of the PH radical is presented. Previous work on the v′ = 0 level found predissociation arising from a spin–orbit induced mixing with a repulsive 5Σ− state correlating to ground state atomic fragments. The v′ = 1 and 2 levels, investigated for the first time here, show a strong Ω, parity and J dependence to the fluorescence lifetime, with low JΩ = 0 e parity levels having greatly elongated lifetimes compared to all the others. We present both experimental measurements of the lifetimes from laser induced fluorescence, and theoretical Fermi golden rule calculations on purely ab initio and experimentally refined potential energy surfaces and spin–orbit coupling matrix elements. MOLPRO 2000.1 was used to calculate all of the adiabatic potentials correlating to the first three atomic asymptotes and the spin–orbit coupling matrix elements between the electronic states involved in the predissociation at the CASSCF and MRCI level. The agreement between the purely ab initio and experimentally observed lifetimes is remarkably good.

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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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