State Key Laboratory of Advanced Textiles Materials and Manufacture Technology, Engineering Research Center for Eco-dyeing and Finishing of Textiles, MOE, Zhejiang Sci-Tech University, Hangzhou, P R China.
J Phys Chem A. 2011 Dec 22;115(50):14282-91. doi: 10.1021/jp2089593. Epub 2011 Nov 29.
Resonance Raman spectra (RRs) for 4,5-ethylenedithio-1,3-dithiole-2-thione (EDDT) were obtained with 397.9 and 416 nm excitation wavelengths, and density functional calculations were performed to elucidate the electronic transitions and the RRs of EDDT in chloroform solvent. The RRs indicate that the Franck-Condon region photodynamics have multidimensional character with nuclear motion predominantly along the C(4)═C(5) stretch and the C(4)═C(5) twist out-of-plane. Resonance Raman cross-sections of A-band absorption have been obtained for the vibrational modes of EDDT with its excitation frequencies spanning the 408 nm. Resonance Raman intensity analysis of the resulting RRs excitation profiles and absorption spectrum using a time-dependent wave packet formalism yields mode-specific nuclear displacement and vibrational reorganizational energies. The intensity analysis results for EDDT were compared to previously reported results for dimethyl 1,3-dithiole-2-thione-4,5-dicarboxylate (DDTD), which shows that the additional six-member heterocycle of EDDT strongly affects the reorganizational energy and energy participation. The authors briefly discuss the differences and similarities of the spectra in terms of molecular symmetry and electron density.
4,5-乙撑二硫代-1,3-二硫杂环戊烯-2-硫酮（EDDT）的共振拉曼光谱（RRs）分别在 397.9nm 和 416nm 的激发波长下获得，通过密度泛函计算阐明了 EDDT 在氯仿溶剂中的电子跃迁和 RRs。RRs 表明，Franck-Condon 区域光动力学具有多维特征，核运动主要沿着 C(4)═C(5)伸缩和 C(4)═C(5)扭转面外进行。用时间相关波包理论对 RRs 激发谱和吸收光谱的 A 带吸收的振动模式进行了共振拉曼截面的研究，得到了 EDDT 的各振动模式的激发频率跨越 408nm。对 RRs 激发谱和吸收光谱的共振拉曼强度分析采用了时间相关波包理论，得到了各模式的核位移和振动重组能。EDDT 的强度分析结果与先前报道的二甲基 1,3-二硫杂环戊烯-2-硫酮-4,5-二羧酸酯（DDTD）的结果进行了比较，结果表明 EDDT 中额外的六元杂环强烈影响了重组能和能量参与。作者简要讨论了分子对称性和电子密度方面光谱的差异和相似性。
