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共轭烯烃的共轭极化势
曹晨忠*,林原斌
作者单位E-mail
曹晨忠* 湖南科技大学化学化工学院,湘潭,411201;湘潭大学化学学院,湘潭,411105 czcao@hnust.edu.cn 
林原斌 湘潭大学化学学院,湘潭,411105  
摘要:
从共轭极化出发,以共轭极化过程的双极态静电能的平均值与非极态静电能的差值作为共轭极化势(CPP).用共轭极化势与共轭烯烃紫外吸收最大波长的能量相关,用量子化学从头计算得到的前线轨道能量与其紫外吸收最大波长的能量进行相关,得到前者与后者相近的结果.进一步以有效极化效应PEI(ef)来定量烷基极化效应对共轭烯烃双极态的稳定作用,并以CPP和PEI(ef)两个变量与共轭烯烃紫外吸收最大波长的能量相关,得到具有良好预测能力的定量方程:ν=1.1746+5.0187CPP-0.43204PEI(ef), R=0.9995, s=0.0403, F=10853.28, n=23研究结果还表明,依靠增加取代基数量的方法来降低紫外吸收能量不及增加共轭链的长度有效.
关键词:  共轭极化  烯烃  共轭极化势  紫外光谱  有效极化效应
DOI:10.1088/1674-0068/17/6/703-710
分类号:
基金项目:
Conjugated Polarizability Potential of Conjugated Alkenes
Cao Chenzhong*,Lin Yuanbin
Abstract:
Based on the conjugated polarization theory,it is expressed as the conjugated polarizability potential (CPP)that the discrepancy between the average electrostatic energy of dipolar state and the electrostatic energy of non-polar state in the conjugated polarizability procedure for the conjugated alkenes. The correlation between CPP and the energy of ultraviolet absorption maximum,and the correlation between the energy of frontier molecular orbital obtained by ab initio calculation of quantum chemistry and the energy of ultraviolet absorption maximum have been carried out for the conjugated alkenes. Both correlation equations show a similar estimated precision. Further, the contribution of alkyl polarizability effect to the stability of dipolar state for the alkyl substituted alkenes with the effective polarizability effect index(PEI(ef))was quantified. Relating the above two parameters CPP and PEI(ef)to the energy of ultraviolet absorption maximum of the substituted alkenes in a two-parameter expression with a good prediction ability was obtained:v=1.1746+5.0187CPP-0.43204PEI (ef),R=0.9995,s=0.0403,F=10853.28,n=23. The investigated results also indicate that it is less effective to reduce the energy of ultraviolet absorption maximum by means of increasing the alkyl substituent groups than lengthening the conjugated backbone chain in the conjugated alkenes.
Key words:  Conjugated polarization,Alkenes,Conjugated polarizability potential,Ultraviolet spectrum,Effective polarizability effect index