Send Robert, Sundholm Dage
Institut für Physikalische Chemie, Universität Karlsruhe, Kaiserstrasse 12, 76128, Karlsruhe, Germany.
Phys Chem Chem Phys. 2007 Jun 14;9(22):2862-7. doi: 10.1039/b616137e. Epub 2007 Apr 3.
The first few excited states of the 11-cis-retinal (PSB11) chromophore have been studied at the coupled-cluster approximative singles and doubles (CC2) level using triple-zeta quality basis sets augmented with double sets of polarisation functions. The two lowest vertical excitation energies of 2.14 and 3.21 eV are in good agreement with recently reported experimental values of 2.03 and 3.18 eV obtained in molecular beam measurements. Calculations at the time-dependent density functional theory (TDDFT) level using the B3LYP hybrid functional yield vertical excitation energies of 2.34 and 3.10 eV for the two lowest states. Zero-point vibrational energy (ZPVE) corrections of -0.09 and -0.17 eV were deduced from the harmonic vibrational frequencies for the ground and excited states calculated at the density functional theory (DFT) and TDDFT level, respectively, using the B3LYP hybrid functional.
使用添加了双组极化函数的三重ζ质量基组，在耦合簇近似单双激发（CC2）水平上研究了11-顺式视黄醛（PSB11）发色团的前几个激发态。2.14和3.21 eV的两个最低垂直激发能与最近报道的分子束测量中获得的2.03和3.18 eV实验值吻合良好。使用B3LYP杂化泛函在含时密度泛函理论（TDDFT）水平上进行的计算给出了两个最低态的垂直激发能分别为2.34和3.10 eV。分别使用B3LYP杂化泛函在密度泛函理论（DFT）和TDDFT水平上计算的基态和激发态的谐振动频率推导出零点振动能（ZPVE）校正值分别为-0.09和-0.17 eV。
