有机化学 ›› 2012, Vol. 32 ›› Issue (01): 121-126.DOI: 10.6023/cjoc1107052 上一篇    下一篇

研究论文

西红花酸二甲酯电子吸收光谱与热力学性质的理论研究

聂汉, 李权, 赵可清   

  1. 四川师范大学化学与材料科学学院 “先进功能材料”四川省高校重点实验室 成都 610068
  • 收稿日期:2011-07-05 修回日期:2011-09-01 出版日期:2012-01-25 发布日期:2011-09-19
  • 通讯作者: 李权 E-mail:liquan6688@163.com
  • 基金资助:

    国家自然科学基金(No. 50973076)、四川省科技计划(No. 2010JY0041)和四川师范大学科研基金(Nos. 09ZDL03, 025156)资助项目.

Theoretical Studies on Electronic Absorption Spectra and Thermodynamic Properties of Crocetin Dimethyl Ester

Nie Han, Li Quan, Zhao Keqing   

  1. Key Laboratory of Advanced Functional Materials, Sichuan Province Higher Education System, College of Chemistry and Material Science, Sichuan Normal University, Chengdu 610068
  • Received:2011-07-05 Revised:2011-09-01 Online:2012-01-25 Published:2011-09-19
  • Contact: Li Quan E-mail:liquan6688@163.com
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 50973076), the Science and Technology Program of Sichuan Province (No. 2010JY0041), and the Scientific Reaserch Foundation of Sichuan Normal University (Nos. 09ZDL03, 025156).

使用密度泛函理论B3LYP 方法, 对西红花酸二甲酯的结构、电子吸收光谱、热力学性质进行理论计算研究, 并基于Tomasi 的极化统一场模型(PCM)讨论溶剂效应. 结果显示, 溶剂对西红花酸二甲酯的前线分子轨道特征几乎无影响, 溶剂作用使该分子的最大吸收波长红移约42 nm, 红移程度与溶剂极性无关. 西红花酸二甲酯分子的气态热力学性质与温度的关系式分别为: CmpΘ =189.782+0.925T, SmΘ =457.503+1.366T, HmΘ =1164.899+0.195T+4.671×10-4T2,GmΘ =1164.899-0.263T-8.989×10-4T2. 298 K 时, 西红花酸二甲酯分子的气态标准摩尔生成焓和标准摩尔生成自由能分别为-1180.67 和-733.23 kJ·mol-1.

关键词: 西红花酸二甲酯, 热力学性质, 吸收光谱, 前线分子轨道, 密度泛函理论

The structures, electronic absorption spectra and thermodynamic properties of crocetin dimethyl ester were calculated by using the density functional theory B3LYP method. Then polarized continuum models of tomasi (PCM) have been used to discuss solvent effects. The computational results showed that solvents have no influence on frontier molecular orbital features of crocetin dimethyl ester and solvents action made the maximum absorption wavelength red-shifted about 42 nm. The relationship formulas between temperature and the gaseous thermodynamic properties of crocetin dimethyl ester are as follows: CmpΘ =189.782+0.925T, SmΘ =457.503+1.366T, HmΘ =1164.899+0.195T+4.671×10-4T2, GmΘ =1164.899-0.263T-8.989×10-4T2. The standard molar formed enthalpy and free energy of crocetin dimethyl ester molecular are respectively -1180.67 and -733.23 kJ·mol-1 at 298.15 K.

Key words: crocetin dimethyl ester, thermodynamic property, absorption spectrum, frontier molecular orbital, density functional theory