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Theoretical Study on Electronic Gain-and-loss Properties of TEMPO and Its Derivates in Charge/Discharge Processes
Shu-cai Mao*,Jin-qing Qu,Kang-cheng Zheng
Author NameAffiliationE-mail
Shu-cai Mao* School of Chemistry and Chemical Engineering, Zhongkai University of Agriculture and Engineering, Guangzhou 510225, China maoshucai@126.com 
Jin-qing Qu School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China  
Kang-cheng Zheng School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China  
Abstract:
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 compu-tational 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.
Key words:  2,2,6,6-tetramethyl-1-piperidinyloxy, Charge/discharge process, Electronic structure, Density functional theory calculation
FundProject:
TEMPO及其衍生物充放电过程中电子得失理论特性
毛淑才*,瞿金清,郑康成
摘要:
在(U)B3LYP/6-31G(d,p)或6-31+G(d,p)基组水平上用密度泛函方法对2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)及其阳离子衍生物在充放电过程中的电子结构和相关性质进行了理论研究. 结果表明在充放电过程中取代基对物质的电子结构和相关性质变化起着重要作用. TEMPO得电子后以单线态存在形式更稳定而阳离子衍生物却以三线态存在形式更稳定. 对TEMPO而言,无论是充电过程还是放电过程对自由基端的N和O的电子特性都有很大影响;对阳离子衍生物而言,放电过程主要影响吡啶端而充电过程主要影响自由基端的变化. 溶剂作用对自由基端的某些键长与电荷分布具有一定影响. 另外,用TDDFT方法对TEMPO及衍生物的紫外吸收光谱进行了计算和模拟,结果与实验数据吻合.
关键词:  TEMPO,充放电过程,电子结构,密度泛函计算
DOI:10.1088/1674-0068/25/02/161-168
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