| Autor: |
Lenzen T; Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany., Manthe U; Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615 Bielefeld, Germany. |
| Jazyk: |
angličtina |
| Zdroj: |
The Journal of chemical physics [J Chem Phys] 2019 Feb 14; Vol. 150 (6), pp. 064102. |
| DOI: |
10.1063/1.5063907 |
| Abstrakt: |
An approach to systematically construct vibronically and spin-orbit coupled diabatic potential energy surfaces (PESs) for X(P) + CH 4 → HX + CH 3 reactions is proposed. Permutational symmetry and permutational invariants of the S 4 group and its S 3 and S 2 × S 2 subgroups are used to construct a diabatic model which properly describes the reaction starting from reactants to products. As a first example, the approach is applied to the construction of diabatic potentials for the F( 2 P) + CH 4 → HF + CH 3 reaction. The description of the entrance channel relies on a set of vibronically and spin-orbit coupled diabatic PESs previously developed by Westermann et al. [Angew. Chem., Int. Ed. 53, 1122 (2014)]. The same set of diabatic electronic states is also used in the transition state region and all four exit channels. There the lowest adiabatic PES derived from the diabatic model reproduces the CSBB-PES of Czakó et al. [J. Chem. Phys. 130, 084301 (2009)]. Interesting aspects of the newly developed diabatic potential matrix and the corresponding adiabatic PESs are discussed. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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