Integrated computational approach to vibrationally resolved electronic spectra: Anisole as a test case
Integrated computational approach to vibrationally resolved electronic spectra: Anisole as a test case
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DOI：
10.1063/1.2943140
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发表时间：
2008-06-28
影响因子：
4.4
通讯作者：
Barone, Vincenzo
中科院分区：
文献类型：
--
作者：
Bloino, Julien;Biczysko, Malgorzata;Barone, Vincenzo
利用一种新的通用的和有效的程序来计算Franck-Condon光谱的第一性原理来阐明苯甲醚的振动分辨光谱的微妙特征。基于密度泛函理论及其含时扩展的电子激发态[B3 LYP/6-311+G（d，p）和TD-B3 LYP/6-311+G（d，p）]的方法被应用于几何优化和谐波频率计算。微扰非谐频率[J. Chem. Phys. 122，014108（2005）]已被计算为基态，和Duschinsky矩阵元素已被用来评估第一激发电子态的相应的非谐校正。在aug-cc-pVDZ基组下，用单点计算方法在耦合团簇（CC）水平上对两个电子态的相对能量进行了修正.理论光谱已被评估使用一个新的优化实现的有效计算的弗兰克-康登因子。理论和实验光谱之间的显着协议允许修改的一些分配的基本振动的苯甲醚的S-1状态。(C)2008年美国物理学会。
A new general and effective procedure to compute Franck-Condon spectra from first principles is exploited to elucidate the subtle features of the vibrationally resolved optical spectra of anisole. Methods based on the density functional theory and its time-dependent extension for electronic excited states [B3LYP/6-311+G(d,p) and TD-B3LYP/6-311+G(d,p)] have been applied to geometry optimizations and harmonic frequency calculations. Perturbative anharmonic frequencies [J. Chem. Phys. 122, 014108 (2005)] have been calculated for the ground state, and the Duschinsky matrix elements have been used to evaluate the corresponding anharmonic corrections for the first excited electronic state. The relative energetics of both electronic states has been refined by single point calculations at the coupled clusters (CC) level with the aug-cc-pVDZ basis set. Theoretical spectra have been evaluated using a new optimized implementation for the effective computation of Franck-Condon factors. The remarkable agreement between theoretical and experimental spectra allowed for revision of some assignments of fundamental vibrations in the S-1 state of anisole. (C) 2008 American Institute of Physics.