电子效应调控丁烯二腈光分子开关的CASSCF和MS-CASPT2理论研究

doi:10.7503/cjcu20150966

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (6): 1128.doi: 10.7503/cjcu20150966

电子效应调控丁烯二腈光分子开关的CASSCF和MS-CASPT2理论研究

曹丹, 李苑莹, 苏青青, 王斌, 刘峰毅(), 王文亮

陕西省大分子科学重点实验室, 陕西师范大学化学化工学院, 西安 710062

收稿日期:2015-12-20 出版日期:2016-06-10 发布日期:2016-05-26
作者简介:联系人简介: 刘峰毅, 男, 博士, 教授, 博士生导师, 主要从事理论与计算化学研究. E-mail:FengyiLiu@snnu.edu.cn
基金资助:
国家自然科学基金(批准号: 21473107, 21473108)、陕西省自然科学基础研究计划项目(批准号: 2015JM2056)和中央高校基本科研业务费专项资金(批准号: GK201502002)资助

CASSCF and MS-CASPT2 Studies on an Electron-tunable,1,2-Dicyanoethylene-based Optical Molecular Switch^†

CAO Dan, LI Yuanying, SU Qingqing, WANG Bin, LIU Fengyi^*(), WANG Wenliang

Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710062, China

Received:2015-12-20 Online:2016-06-10 Published:2016-05-26
Contact: LIU Fengyi E-mail:FengyiLiu@snnu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21473107, 21473108), the Natural Science Basic Research Plan in Shaanxi Province of China(No.2015JM2056) and the Fundamental Research Funds for the Central Universities, China(No.GK201502002)

摘要/Abstract

摘要：

采用多组态CASSCF方法和MS-CASPT2方法研究了丁烯二腈中性分子及阳离子和阴离子的顺-反异构化机理. 结果表明, 中性分子和离子态的光顺-反异构化反应经历不同的非绝热跃迁途径: 中性丁烯二腈受光激发至S₁态后, 需克服一个不低于19.7 kJ/mol的能垒才有机会到达基态和激发态间的圆锥交叉(S₁/S₀-CI), 随后经非辐射跃迁回到基态, S₁/S₀-CI在结构上偏离C═C双键旋转路径, 且能量较高, 因此会降低旋转速度, 阻碍旋转的单向性;丁烯二腈阳离子和阴离子自由基的D₀态和D₁态旋转势能面在90°处相交, 优化的D₁/D₀-CI与D₁态中间体的结构和能量均相近, 因此从D₁态经由D₁/D₀-CI无辐射跃迁到D₀态的过程无势垒, 在此过程中C═C旋转方向性得到最大限度的保持. 研究结果证实了电子诱导不仅能降低基态热旋转势垒, 而且能够调控光旋转的非绝热跃迁机理.

关键词: 顺-反异构, 圆锥交叉, 丁烯二腈, 分子开关

Abstract:

CASSCF and MS-CASPT2 mechanistic studies were carried on the cis-trans isomerization processes of 1,2-dicyanoethylene in its neutral, cationic and anionic forms. The results confirmed the importance of electron-induction in reducing the reaction barrier, and more importantly, revealed the different nonadiabatic channels tuned by electron attachment/detachment. The S₁→S₀ decay of neutral dicyanoethylene need overcome a mild barrier(≥19.7 kJ/mol) to reach a H-migration-type, namely the S₁/S₀-CI, which is away from the C═C torsional coordinates and may slow down the speed of C═C rotation and hurt its directionality; while in cationic and anionic isomerization processes, the D₁ and D₀ PESs intersect along the rotary path, therefore, the nonadiabatic D₁→D₀ decay is barrierless, as result, the directionality of C═C rotation is maintained. The study revealed the role of electron induction in tuning the cis-trans photoisomerization, and shed light on the design of light-driven molecular rotary motors.

Key words: Cis-trans isomerization, Conical intersection, 1, 2-Dicyanoethylene, Molecular switch

中图分类号:

O641

TrendMD:

曹丹, 李苑莹, 苏青青, 王斌, 刘峰毅, 王文亮. 电子效应调控丁烯二腈光分子开关的CASSCF和MS-CASPT2理论研究. 高等学校化学学报, 2016, 37(6): 1128.

CAO Dan, LI Yuanying, SU Qingqing, WANG Bin, LIU Fengyi, WANG Wenliang. CASSCF and MS-CASPT2 Studies on an Electron-tunable,1,2-Dicyanoethylene-based Optical Molecular Switch^†. Chem. J. Chinese Universities, 2016, 37(6): 1128.

图/表 7

Fig.1 Cis-trans isomerization reaction between maleonitrile(cis) and fumaronitrile(trans)

Fig.2 Nature of frontier MOs for cis and trans(A) and representative electronic configurations of ground- and excited states of neutral, cationic and anionic dicyanoethylene(B)

Fig.3 Nature of frontier MOs for cis(A) and trans(C) conformations and variation of MO energies along C1═C1' rotary path(B)a,a'. Anion; b,b'. neutral; c,c'. cation. a—c. MO 20; a'—c'. MO 21.

Fig.4 CASSCF(A), MS-CASPT2//CASSCF(B) and MS-CASPT2(C) computed PESs(potential energy surfaces) of 1,2-dicyanoethylene along rotary path(θ)a. S0-MEP; b. S0//S1; c. S1-MEP; d. S1//S0. The S1//S0 energy profiles indicate the S1-state energies on the basis of optimized S0-state structure(So does S0//S1 curves).

Fig.5 CASSCF-optimized geometry of S1/S0-CI(A) and MS-CASPT2//CASSCF intrapolated S1-min→S1/S0-CI MEP(B, dimensionless) of neutral dicyanoethylene

Fig.6 CASSCF computed PESs for cation(A) and anion(B) dicyanoethylene and the corresponding MS-CASPT2//CASSCF energy profiles for cationic(C) and anionic(D) dicyanoethylene along rotary path(θ)a. D0-MEP; b. D0//D1; c. D1-MEP; d. D1//D0.

Fig.7 Cationic(A1, A2) and anionic(B1, B2) D1-min(A1, B1) and D1/D0-CIs(A2, B2) optimized at the CASSCF/cc-pVTZ level

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电子效应调控丁烯二腈光分子开关的CASSCF和MS-CASPT2理论研究

CASSCF and MS-CASPT2 Studies on an Electron-tunable,1,2-Dicyanoethylene-based Optical Molecular Switch^†

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电子效应调控丁烯二腈光分子开关的CASSCF和MS-CASPT2理论研究

CASSCF and MS-CASPT2 Studies on an Electron-tunable,1,2-Dicyanoethylene-based Optical Molecular Switch†

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CASSCF and MS-CASPT2 Studies on an Electron-tunable,1,2-Dicyanoethylene-based Optical Molecular Switch^†