| Title |
Intensities of KCs S+E(4)1S+ ?(a3S+, X1S+) band system up to dissociation threshold: an interplay between spin-orbit, hyperfine and rovibronic coupling effects |
| ID_Doc |
20003 |
| Authors |
Klincare, I; Tamanis, M; Ferber, R; Pazyuk, EA; Stolyarov, AV; Havalyova, I; Pashov, A |
| Title |
Intensities of KCs S+E(4)1S+ ?(a3S+, X1S+) band system up to dissociation threshold: an interplay between spin-orbit, hyperfine and rovibronic coupling effects |
| Year |
2022 |
| Published |
|
| Abstract |
The relative intensity distribution in the rotationally resolved laser-induced fluorescence spectra belong-ing to the E(4)(1)sigma(+) ->(a(3)sigma(+), X-1 sigma(+)) band systems of the KCs molecule was analyzed. The experimental intensities in doublet P, R progressions assigned to spin-allowed E & RARR;X and spin-forbidden E & RARR;a tran-sitions up to their common ground dissociation limit were described in the framework of a coupled-channels (CC) deperturbation model applied for the interacting X1E+ and a3E+ states. The CC inten-sity simulation was based solely on fixed electronic structure parameters as functions of the internu-clear distance R , namely: accurate empirical potential energy curves for all three states, ab initio esti-mates for matrix elements A(R) of the hyperfine structure (HFS), and transition dipole moments dEX(R) and dEa(R). A comparison between the measured intensities and their theoretical counterparts demon-strates a strong competition between different intramolecular interactions. A weak spin-orbit coupling of the upper E(4)1E+ state with the remote 3 17 states is responsible for appearance of the E & RARR;a vibra-tional bands for the intermediate va-values. In turn, the HFS coupling between X1E+ and a3E+ states leads to peculiarities in E & RARR;(X, a ) intensities, which are pronounced for high vX/a-values in the vicin-ity of K(42S)+Cs(62S) dissociation threshold. Both adiabatic ro-vibrational and non-adiabatic electronic-rotational interactions explain the abrupt deviation of some observed P/R intensity ratios from the ex-pected Honl-London factors.(c) 2022 Elsevier Ltd. All rights reserved. |
| PDF |
https://arxiv.org/pdf/2207.03237
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