Department of Chemistry and State Key Laboratory of ATMMT(MOE), Zhejiang Sci-Tech University, Hangzhou, People's Republic of China 310018.
J Phys Chem B. 2010 Mar 18;114(10):3623-32. doi: 10.1021/jp1000978.
Resonance Raman spectra (RRs) of tetra(4-aminophenyl) porphine (TAPP) were obtained, and density functional calculations were done to help the elucidation of the photorelaxation dynamics of Soret (B(x) and B(y) band) and Q(y) electronic transitions. The RRs indicate that the photorelaxation dynamics for the S(0) --> S(3) excited electronic state is predominantly along the totally symmetric porphin ring C(beta)=C(beta) + C(m)C(alpha) stretch, C(m)-ph stretch, and simultaneously along the asymmetric nu(C(m)C(alpha))(as) and nu(C(alpha)C(beta))(as) relaxation processes leading to Q(y) while that for S(0) --> S(2) is predominantly along the porphin ring C(beta)=C(beta) + C(m)C(alpha) stretch and simultaneously along the asymmetric nu(C(m)C(alpha))(as) + nu(C(alpha)C(beta))(as) relaxation processes leading to thermal equilibrium in Q(x). The excited state structural dynamics of TAPP determined from RRs shows that internal conversion B(x) --> Q(y) electronic relaxation occurs in tens of femtoseconds and the short-time dynamics were first interpreted with account of the time-dependent wave packet theory and Herzberg-Teller contributions.
得到了四(4-氨基苯基)卟啉(TAPP)的共振拉曼光谱(RRs)，并进行了密度泛函计算，以帮助阐明 Soret(B(x)和 B(y)带)和 Q(y)电子跃迁的光致松弛动力学。RRs 表明，S(0) --> S(3)激发电子态的光致松弛动力学主要沿着完全对称的卟啉环 C(beta)=C(beta) + C(m)C(alpha)伸展、C(m)-ph 伸展，同时沿着不对称的 nu(C(m)C(alpha))(as)和 nu(C(alpha)C(beta))(as)松弛过程导致 Q(y)，而 S(0) --> S(2)主要沿着卟啉环 C(beta)=C(beta) + C(m)C(alpha)伸展，同时沿着不对称的 nu(C(m)C(alpha))(as) + nu(C(alpha)C(beta))(as)松弛过程导致 Q(x)中的热平衡。从 RRs 确定的 TAPP 激发态结构动力学表明，B(x) --> Q(y)电子弛豫在数十飞秒内发生，短时间动力学首先通过考虑含时波包理论和 Herzberg-Teller 贡献进行了解释。
