Calculation of the Jahn-Teller effect in benzene cation: Application to spectral analysis
Calculation of the Jahn-Teller effect in benzene cation: Application to spectral analysis
复制标题
苯阳离子中 Jahn-Teller 效应的计算：在光谱分析中的应用
DOI：
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发表时间：
2002
期刊：
影响因子：
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通讯作者：
T. Miller
中科院分区：
文献类型：
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作者：
B. Applegate;T. Miller
Ab initio calculations have been performed for the cations of benzene, C6H6, and its fluorinated analogs, C6F6 and C6H3F3. Calculated molecular parameters characterizing the Jahn-Teller potential energy surface (PES) are very consistent with those derived from the spectra of C6F6+ and C6H3F3+. However the calculated Jahn-Teller stabilization energy for the benzene cation is roughly three times greater than that previously reported experimentally. With the aid of the calculated values, a more complete analysis of the available spectral data for C6H6+ and C6D6+ is performed, with an emphasis on the data from ZEKE experiments and IR spectra of the Ar⋅C6H6+, Ne⋅C6H6+, and Ar⋅C6D6+ complexes. The comprehensive analysis reveals Jahn-Teller activity in 3 e2g modes for C6(H/D)6+ and provides values for their vibrational frequencies, linear and quadratic Jahn-Teller coupling constants, as well as quadratic coupling constants for several other degenerate modes. These new molecular parameters are generally in good a...
