Temporal electronic structure of non-resonant Raman excited virtual state of P-nitroaniline by 514 nm excitation via bond polarisabilities     

王培杰  方炎  吴国祯 《海洋学报(英文版)》2010,29(11)

We have studied the temporal bond polarisabilities of para-nitroaniline from the Raman intensities by the algorithm proposed by Wu et al. in 1987 (Tian B, Wu G, Liu G 1987 J. Chem. Phys. 87 7300). The bond polarisabilities provide much information concerning the electronic structure of the non-resonant Raman excited virtual state. At the initial moment by the 514.5 nm excitation, the tendency of the excited electrons (mapped out by the bond polarisabilities) is to spread to the molecular periphery, and the electronic structure of the Raman virtual state is close to the pseudo-quinonoidic state. When the final stage of relaxation is approached, the bond polarisabilities of those peripheral bonds relax faster than those closer to the molecular core, the phenyl ring. The molecule is in the benzenoidic form as demonstrated by the bond polarisabilities after relaxation.  相似文献   

亚乙基硫脲分子键伸缩模式与全耦合模式键极化率的对比及其拉曼激发虚态的相关研究          下载免费PDF全文

陈艳荣  王培杰  方炎 《海洋学报》2010,32(9):6052-6058

从拉曼峰强着手,得到了键伸缩模式与全耦合模式两种不同计算条件下,亚乙基硫脲(ethylene thiourea,ETU)分子的键极化率,并比较分析了两种计算结果的异同.研究表明:在键伸缩模式的算法中,仅考虑势能分布中键对称伸缩比重相对较大的部分拉曼峰参与极化率计算,显然忽略了键伸缩与键弯曲间的相互耦合,造成了与弯曲振动耦合较强的部分键伸缩极化率值存在一定误差.因此,此方法虽能使问题简化,但却丢失了一些信息.而全耦合模式算法考虑了所有振动模式(键伸缩与键弯曲)相互影响的情况,能更全面的反映键电荷的分布情况,  相似文献