Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5376769 | Chemical Physics | 2006 | 11 Pages |
Abstract
The vibronic coupling between 2Î and 2Σ electronic states of a linear molecule is considered with the inclusion of the spin-orbit coupling of the 2Î electronic state, employing the microscopic (Breit-Pauli) spin-orbit coupling operator in the single-electron approximation. The 6 Ã 6 Hamiltonian matrix in a diabatic spin-electronic basis is derived by an expansion of the molecular Hamiltonian in powers of the bending amplitude up to second-order. The symmetry properties of the Hamiltonian are analyzed. It is pointed out that there exist zeroth-, first-, and second-order Σ-Î vibronic-coupling terms of spin-orbit origin, which are absent when the usual phenomenological form of the spin-orbit coupling operator is used instead of its microscopic form. The influence of the Σ-Î and spin-orbit vibronic-coupling terms on the adiabatic potential energy curves as well as on the vibronic spectra is analyzed for selected models. It is demonstrated that the interplay of strong Σ-Î vibronic-coupling and strong spin-orbit splitting of the Î state can result in unexpectedly complex vibronic spectra.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Sabyashachi Mishra, Wolfgang Domcke, Leonid V. Poluyanov,