کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
5376769 1504332 2006 11 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Study of strong Σ-Π and spin-orbit vibronic coupling effects in linear triatomic molecules
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
Study of strong Σ-Π and spin-orbit vibronic coupling effects in linear triatomic molecules
چکیده انگلیسی
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 × 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.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volume 327, Issues 2–3, 11 September 2006, Pages 457-467
نویسندگان
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