喷气冷却邻氟苯甲醚的荧光光谱：通过杜斯基尼效应和费米共振混合。

Fluorescence spectroscopy of jet-cooled o-fluoroanisole: mixing through Duschinsky effect and Fermi resonance.

机构信息

Department of Chemistry and Materials Science, Tokyo Institute of Technology, 2-12-1 Ohokayama, Meguro, Tokyo 152-8551, Japan.

出版信息

J Chem Phys. 2010 Jun 7;132(21):214308. doi: 10.1063/1.3442490.

DOI:10.1063/1.3442490

PMID:20528023

Abstract

Laser-induced fluorescence (LIF) excitation, UV-UV hole burning, and single vibronic level fluorescence (SVLF) spectra of jet-cooled o-fluoroanisole (o-FA) were measured. The most intense lowest-frequency band at 36 612 cm(-1) was assigned to the origin band of the most stable trans conformer. The UV-UV hole-burning spectrum demonstrated that the prominent bands in the LIF excitation spectrum were responsible for the trans conformer. The metastable non-planar conformer was not observed in the spectra. The vibrational band assignments were performed with the aid of quantum chemical calculations at the B3LYP/cc-pVTZ and CIS/6-311G(d,p) levels. The precise analysis of the SVLF spectra indicated that strong vibrational mixing through the Duschinsky effect and the Fermi resonance occurs in the S(1) state.

摘要

激光诱导荧光（LIF）激发、紫外-紫外光烧孔和单振子荧光（SVLF）光谱技术被用于测量喷射冷却的邻氟苯甲醚（o-FA）。在 36612cm(-1) 处的最强的最低频率带被分配到最稳定的反式构象的起始带。紫外-紫外光烧孔光谱表明，LIF 激发光谱中的显著带归因于反式构象。在光谱中没有观察到亚稳的非平面构象。振动带分配是在 B3LYP/cc-pVTZ 和 CIS/6-311G(d,p) 水平的量子化学计算的帮助下完成的。对 SVLF 光谱的精确分析表明，在 S(1)态中通过 Duschinsky 效应和费米共振发生强烈的振动混合。