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Nonadiabatic coupling of the 1 1A″ and 2 1A″ states of ozone

Publication Type : Journal Article

Thematic Areas : Center for Computational Engineering and Networking (CEN)

Source : Chemical Physics Volume 194, Issue 1, 1 May 1995

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Campus : Coimbatore

School : School of Engineering

Center : Center for Computational Engineering and Networking, Computational Engineering and Networking

Department : Center for Computational Engineering and Networking (CEN)

Year : 1995

Abstract : We report the results of ab initio calculations of the nonadiabatic Born coupling terms for the two lowest-lying singlet A″ excited states of ozone (1A2 and 1B1 in C2v symmetry) whose electronic potential energy surfaces exhibit a crossing at a bond angle near 120°. Since photoexcitation from the ground state to these A″ states is believed to be responsible for the Chappuis band of ozone, determination of the nonadiabatic coupling terms in the molecular Hamiltonian is therefore likely to be of importance in understanding the predissociative features of the spectrum. The nuclear derivative coupling matrix elements are computed between ab initio electronic wavefunctions obtained from multi-reference configuration interaction (MRD-CI) calculations in a basis of configuration state functions constructed from MCSCF orbitals. The first-derivative nonadiabatic coupling terms are calculated analytically in a manner similar to the calculation of analytic energy gradients, thereby avoiding the cumbersome numerical differentiation of CI and SCF coefficients. The calculated analytical derivative coupling matrix elements are used to determine a suitable transformation to a quasidiabatic basis.

Cite this Research Publication : Thomas Neuheuser, N. Sukumar and S. D. Peyerimhoff, “Nonadiabatic Coupling of the 1A” and 2A” States of Ozone”, Chem. Phys. 194, 45-64 (1995) IF: 1.652

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