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Mishra, Sabyashachi; Domcke, Wolfgang; Poluyanov, Leonid V., E-mail: sabyashachi.mishra@ch.tum.de2006
AbstractAbstract
[en] The vibronic coupling between 2Π and 2Σ electronic states of a linear molecule is considered with the inclusion of the spin-orbit coupling of the 2Π electronic state, employing the microscopic (Breit-Pauli) spin-orbit coupling operator in the single-electron approximation. The 6 x 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-Π 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-Π 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-Π vibronic-coupling and strong spin-orbit splitting of the Π state can result in unexpectedly complex vibronic spectra
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S0301-0104(06)00308-9; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
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Journal Article
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