The electronic spectrum of pyrrole
The electronic spectrum of pyrrole
复制标题
吡咯的电子能谱
DOI：
10.1063/1.479332
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发表时间：
1999
影响因子：
4.4
通讯作者：
P. Jørgensen
中科院分区：
文献类型：
--
作者：
O. Christiansen;J. Gauss;J. Stanton;P. Jørgensen
通过使用由CCS、CC2、CCSD和CC3组成的耦合簇模型进行计算，研究了吡咯的电子能谱。基集效应已经通过使用相关一致基集进行计算来研究，这些基集增加了专门为描述里德伯态而设计的函数。振荡强度、激发态偶极矩和电子电荷分布的第二矩被用来表征电子跃迁和最终态。计算了几种选定状态的结构和振动频率，并强调了区分垂直和绝热跃迁的重要性，以便与实验进行准确比较。实验光谱在相关能量区域进行了仔细检查，并对最近计算[CASPT2， MRMP， ADC(2)]的准确性进行了严格的重新检查。
The electronic spectrum of pyrrole has been investigated by performing calculations using a hierarchy of coupled-cluster models consisting of CCS, CC2, CCSD, and CC3. Basis-set effects have been investigated by carrying out calculations using correlation-consistent basis sets augmented with functions especially designed for the description of Rydberg states. Oscillator strengths, excited state dipole moments, and second moments of the electronic charge distributions have been used to characterize the electronic transitions and final states. Structures and vibrational frequencies have been calculated for a few selected states, and the importance of distinguishing between vertical and adiabatic transitions for accurate comparison with experiment has been emphasized. The experimental spectrum has been scrutinized in the relevant energy region, and the accuracy of recent calculations [CASPT2, MRMP, ADC(2)] has been critically reexamined.