Department of Chemistry and State Key Laboratory of ATMMT(MOE), Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China.
Spectrochim Acta A Mol Biomol Spectrosc. 2011 May;78(5):1416-23. doi: 10.1016/j.saa.2011.01.020. Epub 2011 Feb 15.
Resonance Raman spectra of free-base octaethylporphine (OEP) were obtained with 368.9 nm, 397.9 nm and 416.0 nm excitation wavelengths, and density functional calculations were done to help the elucidation of Soret (B(x) and B(y)-band) electronic transitions and the corresponding photo relaxation dynamics of OEP. The RRs indicate that the Franck-Condon region photo relaxation dynamics upon S(0)→S(8) electronic transition is predominantly along the totally symmetric C(m)C(α) stretch, the C(β)C(β) stretch, and simultaneously along the asymmetric δ(pyr deformation),γ(CH(2)) vibrational relaxation processes. The excited state structural dynamics of OEP determined from resonance Raman spectra show that the internal conversion between B(y) and B(x) electronic states occurs in tens of femtoseconds and the electronic relaxation dynamics were firstly interpreted with account of the time-dependent wave packet theory and Herzberg-Teller (vibronic coupling) contributions.
用 368.9nm、397.9nm 和 416.0nm 激发波长获得了游离基八乙基卟啉（OEP）的共振拉曼光谱，并进行了密度泛函计算，以帮助阐明 Soret（B(x) 和 B(y)-带）电子跃迁和 OEP 的相应光致松弛动力学。RRs 表明，S(0)→S(8)电子跃迁时 Franck-Condon 区域光致松弛动力学主要沿完全对称的 C(m)C(α)拉伸、C(β)C(β)拉伸以及同时沿不对称的 δ(pyr 变形)、γ(CH(2))振动松弛过程进行。从共振拉曼光谱确定的 OEP 的激发态结构动力学表明，B(y)和 B(x)电子态之间的内转换发生在几十飞秒内，并且首先考虑了含时波包理论和 Herzberg-Teller（振子耦合）贡献来解释电子弛豫动力学。
