Ab initio characterization of the S1-S2 conical intersection in pyrazine and calculation of spectra
Ab initio characterization of the S1-S2 conical intersection in pyrazine and calculation of spectra
复制标题
吡嗪中 S1-S2 锥形交点的从头算表征及光谱计算
DOI：
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发表时间：
1992
期刊：
影响因子：
--
通讯作者：
W. Domcke
中科院分区：
文献类型：
--
作者：
L. Seidner;G. Stock;A. Sobolewski;W. Domcke
在自洽场、二阶Mo/ller-Plesset（SCF/MP2）水平上，计算了吡嗪三个最低单重态的势能函数，作为从头算确定的基态简正坐标的函数.电子结构计算证实了S1（nπ*）和S2（ππ*）表面在后者表面的最小值附近存在圆锥相交。基于从头算数据，建立了一个包含四个光谱活性振动模式的电子振动耦合模型。使用先前开发的方法计算该模型的吸收、共振-拉曼、荧光和飞秒时间分辨泵浦-探测光谱。结果与实验数据进行了比较。
Potential‐energy functions of the three lowest singlet states of pyrazine have been computed on the self‐consistent field, second‐order Mo/ller–Plesset (SCF/MP2) level as a function of ab initio determined ground‐state normal coordinates. The electronic‐structure calculations confirm the existence of a conical intersection of the S1(nπ*) and S2(ππ*) surfaces near the minimum of the latter surface. A vibronic‐coupling model involving four spectroscopically active vibrational modes is constructed on the basis of the ab initio data. Absorption, resonance‐Raman, fluorescence, and femtosecond time‐resolved pump–probe spectra are computed for this model using previously developed methods. The results are compared with experimental data where available.
影响因子：
14.7
作者：
S. Asher
通讯作者：
S. Asher