Theoretical study on the electronic structures and related properties of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and its cationic lipid derivates in the charge/discharge processes has been carried out using the density functional theory (DFT) at the (U)B3LYP/6-31G(d,p) or 6-31+G(d,p) level. The changes and regularities of geometric and electronic properties of these compounds in the charge/discharge processes were revealed in detail. The computational results show that the substitute group plays a very important role in the electronic structures and related properties of TEMPOs during the charge/discharge processes. It is very interesting to find that after getting an electron, TEMPO is more stable in singlet state but the lipid is more stable in triplet state. For TEMPO, both the charge and the discharge processes greatly influence the electronic properties of N and O atoms of the radical part. For the cationic lipid, the discharge process mainly influences the pyridinium head and the charge process mainly influences the free radical head. Moreover, the solvent effect plays an important role in some bond lengths and the charge population of the free radical head. In addition, the UV-Vis absorption spectra of TEMPO and the lipid were calculated and simulated using TDDFT at the 6-31G(d,p) or 6-31+G(d,p) level, in satisfying agreement with the experimental ones.
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April 2012
Research Article|
April 01 2012
Theoretical Study on Electronic Gain-and-loss Properties of TEMPO and Its Derivates in Charge/Discharge Processes
Shu-cai Mao;
Shu-cai Mao
1School of Chemistry and Chemical Engineering, Zhongkai University of Agriculture and Engineering, Guangzhou 510225
China
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Jin-qing Qu;
Jin-qing Qu
2School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640
China
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Kang-cheng Zheng
Kang-cheng Zheng
3School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275
China
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Chin. J. Chem. Phys. 25, 161–168 (2012)
Article history
Received:
November 30 2011
Accepted:
February 12 2012
Citation
Shu-cai Mao, Jin-qing Qu, Kang-cheng Zheng; Theoretical Study on Electronic Gain-and-loss Properties of TEMPO and Its Derivates in Charge/Discharge Processes. Chin. J. Chem. Phys. 1 April 2012; 25 (2): 161–168. https://doi.org/10.1088/1674-0068/25/02/161-168
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