Abstract
In this study, a vibronic matrix that describes the singlet-triplet interaction of the 1Π and 3Σ– terms in linear triatomic molecules is obtained. The analysis is carried out taking into account the spin-orbit interaction in the electronic Hamiltonian and is based on the use of its symmetry properties. It is shown that the symmetry operators of the electron Hamiltonian contain both spatial operations (acting on the coordinates of electrons) and matrix operations (acting on the electron spins). The study takes into account only deformation π-modes, and the resulting \(5 \times 5\) vibronic matrix actually describes the relativistic pseudo-Renner effect \(\left( {^{1}{{\Pi }}{{ + }^{3}}{{{{\Sigma }}}^{ - }}} \right) \times \pi .\) The eigenvalues of the vibronic matrix (i.e., potential energy surface) are invariants of the \({{C}_{{\infty {v}}}}\) group. The vibronic matrix contains five parameters of electrostatic origin and five parameters due to the spin-orbit interaction.
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Funding
This study was carried out on the topic of a state assignment (registration number AAAA-A19-119071190017-7).
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Poluyanov, L.V., Ushakov, V.G. Singlet-Triplet Interaction of the 1Π And 3Σ– Terms in Linear Triatomic Molecules. Russ. J. Phys. Chem. B 15, 407–412 (2021). https://doi.org/10.1134/S1990793121030106
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DOI: https://doi.org/10.1134/S1990793121030106