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Theoretical Study on Resonance Raman Spectra of Tetraoxaporphyrin Dication by TDDFT Calculation
Guo-bing Wang,Hui-qing Zhao,Zhen-lin Zhang,Wen-lou Wang,Dong-ming Chen*
Author NameAffiliationE-mail
Guo-bing Wang Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Hui-qing Zhao Department of Chemistry, College of Basic Medicine, Anhui Medical University, Hefei 230032, China  
Zhen-lin Zhang Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Wen-lou Wang Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Dong-ming Chen* Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China dmchen@ustc.edu.cn 
Abstract:
The B state excited resonance Raman scattering of tetraoxaporphyrin dication (TOP2+) was theoretically studied with DFT/TDDFT calculations and the sum-over-states approach of polarizability including both the A and B terms contributions. The resonance Raman spectra calculated with PBE1PBE, B3LYP, Cam-B3LYP, and B3LYP-D3 functionals are similar to each other in general, with PBE1PBE and B3LYP being better in reproducing resonance Raman intensities in comparison with the experiment. The calculated relative intensities of the totally symmetric modes are excellently consistent with the experiment. The TDDFT calculations manifested a considerable deformation of the B state along theυ2,υ6, υ7, and υ8 modes, which is responsible for the strong resonance Raman intensities of these modes. The resonance Raman intensities of non-totally symmetric modes were calculated to be weaker than the totally symmetric modes by one or two order of magnitude, which qualitatively agrees with the experiment. However, the resonance Raman intensity of the υ10 mode (CβCβ stretch, B1g symmetry) predicted by TDDFT calculations is unexpectedly small whereas that of the υ11 mode (symmetric CαCm stretch, B1g symmetry) is too large, which is assumed to be caused by the Jahn-Teller instability for the B state of TOP2+.
Key words:  Tetraoxaporphyrin, Resonance Raman, TDDFT, Excited state structure, Franck-Condon mechanism
FundProject:
四氧杂卟啉二价正离子共振拉曼光谱的TDDFT计算研究
王国兵,赵慧卿,章振林,王文楼,陈东明*
摘要:
采用DFT/TDDFF计算和极化率的态求和方法研究了四氧杂卟啉二价正离子(TOP2+)B态(S2态)激发的共振拉曼(RR)光谱, 计算模型同时处理了A项和B项对拉曼极化率的贡献.用PBE1PBE、B3LYP、Cam-B3LYP、B3LYP-D3四种交换-相关泛函计算得到的RR光谱总体上相似,其中PBE1PBE和B3LYP 给出的RR 强度与实验吻合得更好一些. 对于全对称振动(A1g),其拉曼谱带相对强度的理论计算结果与实验一致;TDDFF计算表明: 相对于基态,TOP2+的B态沿υ2、υ6、υ7、υ8简正模式有较大的无量纲位移, 导致相应的RR带有较大的强度. 非全对称的B1g和B2g 模式通过B项机理增强,其强度比A1g模式小1~2个量级,与实验结果定性符合. 与实验相比,υ10模式(B1g)RR强度的理论值过小,而υ11模式(B1g)的理论值偏大;这可能是由于TOP2+的B-态(S2态)具有Jahn-Teller效应.
关键词:  四氧杂卟啉,共振拉曼光谱,TDDFT,Franck-Condon机理,激发态结构
DOI:10.1063/1674-0068/28/cjcp1504067
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