Infrared Absorption Measurements of Conjugated Radical Ion Dimers and Analyses of Electron-Molecular Vibration Interactions

本文研究了2，5“-二（甲硫基）三噻吩自由基阳离子、二聚体和二价阳离子以及[3_4]（1，2，4，5）环蕃自由基阳离子的红外吸收光谱。采用密度泛函理论（DFT）方法，在B3 LYP/6-311+G** 水平上计算了2，5“-双（甲硫基）三噻吩的中性分子、自由基阳离子和双阳离子以及[3_4]（1，2，4，5）环蕃的中性分子和自由基阳离子的结构和振动性质（谐波频率、振动模式和红外强度）.我们比较了红外光谱的观测值和密度泛函理论的计算值，并分析了电子与分子的振动相互作用。分子振动模式，诱导分子内和分子间的电荷通量观察到大的红外吸收强度。

Infrared absorption spectra were observed for (1) radical cation, its dimer, and dication of2,5''-bis(methylthio)terthiophene and (2) radical cation of [3_4](1,2,4,5)cyclophane. The structures and vibrational properties (harmonic frequencies, vibrational patterns, and infrared intensities) were calculated for (1) the neutral molecule, radical cation and dication of 2,5''-bis(methylthio)terthiophene and (2) the neutral molecule and radical cation of [3_4](1,2,4,5)cyclophane by DFT method at B3LYP/6-311+G** level. We compared the observed infrared spectra with those calculated by DFT method and analyzed electron-molecular vibration interaction. The molecular vibrational modes which induce both intramolecular and intermolecular charge fluxes were observed with large infrared absorption intensities.