Spin-orbit vibronic coupling in 3Pi states of linear triatomic molecules |
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Authors: | Mishra Sabyashachi Poluyanov Leonid V Domcke Wolfgang |
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Affiliation: | Department of Chemistry, Technical University of Munich, D-85747 Garching, Germany. sabyashachi.mishra@ch.tum.de |
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Abstract: | The Renner-Teller vibronic-coupling problem of a 3Pi electronic state of a linear molecule is analyzed with the inclusion of the spin-orbit coupling of the 3Pi electronic state, employing the microscopic (Breit-Pauli) spin-orbit coupling operator for the two unpaired electrons. The 6x6 Hamiltonian matrix in a diabatic spin-electronic basis is obtained by an expansion of the molecular Hamiltonian in powers of the bending amplitude. The symmetry properties of the Hamiltonian with respect to the time-reversal operator and the relativistic vibronic angular momentum operator are analyzed. It is shown that there exists a linear vibronic-coupling term of spin-orbit origin, which has not been considered so far in the Renner-Teller theory of 3Pi electronic states. While two of the six adiabatic electronic wave functions do not exhibit a geometric phase, the other four carry nontrivial topological phases which depend on the radius of the integration contour. The spectroscopic effects of the linear spin-orbit vibronic-coupling mechanism have been analyzed by numerical calculations of the vibronic spectrum for selected model examples. |
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