Theoretical study of the Coriolis effect in LiNa, LiK, and LiRb molecules
| Autor: | Robert Moszynski, E. A. Bormotova, I. Majewska, E. A. Pazyuk, S. V. Kozlov, Andrey V. Stolyarov |
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| Rok vydání: | 2021 |
| Předmět: |
Physics
Ab initio General Physics and Astronomy 02 engineering and technology Configuration interaction 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Diatomic molecule Molecular physics Dissociation (psychology) 0104 chemical sciences Matrix (mathematics) Physics::Atomic and Molecular Clusters medicine Physical and Theoretical Chemistry Multiplicity (chemistry) medicine.symptom Perturbation theory 0210 nano-technology Wave function |
| Zdroj: | Physical Chemistry Chemical Physics. 23:5187-5198 |
| ISSN: | 1463-9084 1463-9076 |
| Popis: | The non-adiabatic electronic matrix elements, LΠΣ(R), that arise from the spin-conserving electron-rotational interactions between all mΣ+ and mΠ states, where multiplicity m = 1, 3, converging to the lowest three dissociation limits of Li-containing alkali diatomics, LiM (M = Na, K, Rb), were calculated ab initio up to large internuclear distances, R. The required electronic wavefunctions were obtained within the framework of the multi-reference configuration interaction treatment of the two-valence-electron problem constructed using small-core scalar-relativistic effective core potentials and l-independent core-polarization potentials. A least squares analysis of the ab initio functions at large internuclear distances in conjunction with long-range perturbation theory (LRPT) revealed three different asymptotic behaviors of the LΠΣ(R → +∞)-functions: const. + β[n]/Rn, characterized by n = -1, 3 and 6. The asymptotic coefficients β[n], extracted from the point-wise ab initio data, were found to be in agreement with their LRPT counterparts, which were evaluated analytically using the relevant atomic parameters. The mass dependence of the LΠΣ matrix elements was investigated analytically and numerically. To confirm the reliability of the LΠΣ(R)-functions and interatomic potentials at small and intermediate distances, the empirical q-factors available for the D1Π-states of all LiM molecules studied were compared with their theoretical counterparts derived from the present ab initio data. |
| Databáze: | OpenAIRE |
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