کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
5376634 1504320 2007 13 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Multi-state vibronic interactions in the fluorobenzene radical cation: The importance of quadratic coupling terms
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
Multi-state vibronic interactions in the fluorobenzene radical cation: The importance of quadratic coupling terms
چکیده انگلیسی
The multi-mode multi-state vibronic interactions in the set of X∼2B1-D∼2A1 electronic states of the monofluoro benzene radical cation are investigated theoretically, based on a quadratic vibronic coupling approach. The underlying ionization potentials and coupling constants are obtained from ab initio coupled-cluster calculations. Previous investigations (relying on the linear coupling approach) are extended by including all (diagonal) quadratic coupling constants for the totally symmetric modes in the five coupled electronic states. The inclusion of these quadratic couplings is found to be essential to correctly reproduce the low-energy conical intersections between different sets of electronic states. The photoelectron, mass-analyzed threshold ionization and photoinduced Rydberg ionization spectra are re-analyzed. The lowering of the minimum energies of intersection is shown to be crucial to lead to an efficient population transfer from higher excited states of the cation to the ground state. The implications of these findings for understanding the fluorescence dynamics of fluorinated benzene radical cations are discussed.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volume 338, Issues 2–3, 25 September 2007, Pages 207-219
نویسندگان
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