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J Chem Phys. 2017 Apr 14;146(14):144110. doi: 10.1063/1.4979949.

An improved spin-orbit coupling model for use within the effective relativistic coupling by asymptotic representation (ERCAR) method.

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Theoretische Chemie, Universit├Ąt Bielefeld, Postfach 100131, D-33501 Bielefeld, Germany.


An improved atomic spin-orbit model is presented, which is designed to be used within the framework of the effective relativistic coupling by asymptotic representation method. This method is used for the generation of highly accurate coupled potential energy surfaces (PESs) to represent the fine structure energies of appropriate systems. The approach is demonstrated using CH3I and its photodissociation as a typical example. The method is based on a specific diabatization of electronic spin-space ("spin-free") states with respect to the asymptote at which a single relativistic atom is separated from a molecular non-relativistic fragment. Thus, the relativistic coupling effects can be treated entirely within the atomic framework. So far, an effective spin-orbit coupling operator which only accounts for intra-state coupling within each atomic spin-space state was used. In the present work, this approach is extended to account for inter-state couplings among different atomic spin-space states as well. It is shown that this extended approach improves the accuracy of the PESs significantly for higher excited states and also enhances the accuracy of low energy states. In particular, it improves the representation of the spin-orbit induced conical intersection among the 3Q0 and 1Q1 states of CH3I, which is of high relevance for the nonadiabatic quantum dynamics of the photodissociation.


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