Lin Na, Zhao Xian, Rizzo Antonio, Luo Yi
Institute of Crystal Materials, Shandong University, 250100 Jinan, Shandong, People's Republic of China.
J Chem Phys. 2007 Jun 28;126(24):244509. doi: 10.1063/1.2745794.
Both the electronic and the vibronic contributions to one- and two-photon absorption of a D-pi-D charge-transfer molecule (4-dimethylamino-4'-methyl-trans stilbene) are studied by means of density functional response theory combined with a linear coupling model. Vibronic profiles of the first four excited states are fully explored. The dominating vibrational modes for both Franck-Condon and Herzberg-Teller contributions are identified. The Franck-Condon contribution dominates the spectra of first, second, and fourth excited states. The Herzberg-Teller contribution is on the other hand of comparable size for the third excited state, where its inclusion leads to a blueshift with respect to the vertical transition. A similar vibronic coupling behavior is found for both one- and two-photon absorptions.
通过密度泛函响应理论结合线性耦合模型，研究了D-π-D电荷转移分子（4-二甲基氨基-4'-甲基反式芪）的单光子和双光子吸收的电子和振子贡献。全面探索了前四个激发态的振子谱。确定了弗兰克-康登和赫兹伯格-泰勒贡献的主要振动模式。弗兰克-康登贡献主导了第一、第二和第四激发态的光谱。另一方面，赫兹伯格-泰勒贡献对于第三激发态具有相当的大小，其包含导致相对于垂直跃迁的蓝移。在单光子和双光子吸收中都发现了类似的振子耦合行为。
