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Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory
Yu-ling Chu1, Zhong Yang1, Zhe-feng Pan2, Jing Liu3, Yue-yi Han3, Yong Ding*3, Peng Song*3
1.Physical and Electronic and Information Engineering Institute, Chifeng University, Chifeng 024001, China;2.Department of Science, Shenyang Aerospace University, Shenyang 110136, China;3.Department of Physics, Liaoning University, Shenyang 110036, China
Abstract:
Density functional theory and time-dependent density-functional theory have been used to investigate the photophysical properties and relaxation dynamics of dimethylaminobenzophe-none (DMABP) and its hydrogen-bonded DMABP-MeOH dimer. It is found that, in non-polar aprotic solvent, the transitions from S0 to S1 and S2 states of DMABP have both n→π* and π→π* characters, with the locally excited feature mainly located on the C=O group and the partial CT one characterized by electron transfer mainly from the dimethylaminophenyl group to the C=O group. But when the intermolecular hydrogen bond C=O…H-O is formed, the highly polar intramolecular charge transfer character switches over to the first excited state of DMABP-MeOH dimer and the energy difference between the two low-lying electronically excited states increases. To gain insight into the relaxation dynamics of DMABP and DMABP-MeOH dimer in the excited state, the potential energy curves for con-formational relaxation are calculated. The formation of twisted intramolecular charge trans-fer state via diffusive twisting motion of the dimethylamino/dimethylaminophenyl groups is found to be the major relaxation process. In addition, the decay of the S1 state of DMABP-MeOH dimer to the ground state, through nonradiative intermolecular hydrogen bond stretching vibrations, is facilitated by the formation of the hydrogen bond between DMABP and alcohols.
Key words:  Hydrogen-bond, Intramolecular charge transfer, Relaxation dynamic, Twisting dynamic
FundProject:
采用密度泛函理论研究二甲基胺-二苯甲酮的分子内电荷转移激发态氢键
初玉玲1, 杨忠1, 潘哲峰2, 刘晶3, 韩岳洢3, 丁勇*3, 宋朋*3
1.赤峰学院物理与电子信息工程系,赤峰024001;2.沈阳航空航天大学理学院,沈阳110136;3.辽宁大学物理学院,沈阳110036
摘要:
利用(含时)密度泛函理论研究了二甲基胺-二苯甲酮(DMABP)及其氢键二聚物DMABP-MeOH的光物理性质和弛豫动力学过程. 结果表明,在非极性和非质子性溶剂中,DMABP分子的第一和第二激发态跃迁同时具有局域激发和分子内电荷转移的特征;在极性质子性溶剂中,分子间氢键C=O…H-O的形成增加了这两个最低激发态之间的能量差,使DMABP-MeOH的第一激发态具有较强极性的分子内电荷转移特性. 通过计算DMABP和DMABP-MeOH分子的激发态构型弛豫势能曲线研究了激发态动力学弛豫过程. 结果表明,通过扭
关键词:  氢键,分子内电荷转移,弛豫动力学,扭转动力学
DOI:10.1088/1674-0068/25/06/654-658
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