| 溶液和熔化状态下分子间的能量传递 |
| |
| 引用本文： | 沈宇能,蒋博,葛传琦,邓罡华,陈海龙,杨学明,袁开军,郑俊荣. 溶液和熔化状态下分子间的能量传递[J]. 化学物理学报, 2016, 29(4): 407-417 |
| |
| 作者姓名： | 沈宇能 蒋博 葛传琦 邓罡华 陈海龙 杨学明 袁开军 郑俊荣 |
| |
| 作者单位： | 中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 大连 116023;中国科学院大学, 北京 100049,莱斯大学化学系, 休斯顿,中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 大连 116023;辽宁师范大学物理和电子工程系, 大连 116029,中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 大连 116023,莱斯大学化学系, 休斯顿,中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 大连 116023,中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 大连 116023,莱斯大学化学系, 休斯顿 |
| |
| 基金项目： | This work was supported by the National Natural Science Foundation of China (No.21373213), the Chinese Academy of Sciences, and the Ministry of Science and Technology. Jun-rong Zheng is supported by the AFOSR Award No.FA9550-11-1-0070, the Welch foundation under Award No.C-1752, the David and Lucile Packard Foundation for a Packard fellowship, and the Alfred P. Sloan Foundation for a Sloan fellowship. |
| |
| 摘 要： | 通过二维红外光谱研究了GdmSCN/KSCN=1/1，GdmSCN/KS13CN=1/1和GdmSCN/KS13C15N=1/1三种混合晶体在熔融和溶液状态下的共振和非共振的分子间振动能量传递的性质. 在这些样品中，给体/受体的能量差越大，能量传递越慢. 而能量传递的快慢与拉曼光谱无关. 非共振能量传递与给体/受体的能量差的关系不能用声子补偿的机理来描述. 相反，它们的关系却可以用退相位机理来定量描述. 在熔融状态下，共振和非共振能量速率与温度的依赖关系也与退相位机理的预测相符合. 这一系列的结果表明只要分子的运动(平动和转动)远远快于非共振能量传递速率，那么退相位机理不仅在溶液中占主导，而且在熔融状态下(纯液体，不含溶剂)也占主导.
|
| 关 键 词： | 振动能量传递 二维红外光谱 声子补偿机理 去相位机理 |
| 收稿时间： | 2016-02-25 |
| 修稿时间： | 2016-04-06 |
Intermolecular Vibrational Energy Transfers in Melts and Solutions |
| |
| Yu-neng Shen,Bo Jiang,Chuan-qi Ge,Gang-hua Deng,Hai-long Chen,Xue-ming Yang,Kai-jun Yuan and Jun-rong Zheng. Intermolecular Vibrational Energy Transfers in Melts and Solutions[J]. Chinese Journal of Chemical Physics, 2016, 29(4): 407-417 |
| |
| Authors: | Yu-neng Shen Bo Jiang Chuan-qi Ge Gang-hua Deng Hai-long Chen Xue-ming Yang Kai-jun Yuan Jun-rong Zheng |
| |
| Affiliation: | State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;University of the Chinese Academy of Sciences, Beijing 100049, China,Department of Chemistry, Rice University, Houston, Texas, USA,State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;School of Physics and Electronic Technology, Liaoning Normal University, Dalian 116029, China,State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China,Department of Chemistry, Rice University, Houston, Texas, USA,State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China,State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China and Department of Chemistry, Rice University, Houston, Texas, USA |
| |
| Abstract: | Resonant and nonresonant intermolecular vibrational energy transfers in Gdm-SCN/KSCN=1/1, GdmSCN/KS13CN=1/1 and GdmSCN/KS113C15N=1/1 mixed crystals in melts and in aqueous solutions are studied with the two dimensional infrared spectroscopy. The energy transfers in the samples are slower with a larger energy donor/acceptor gap, independent of the Raman spectra. The energy gap dependences of the nonresonant energy transfers cannot be described by the phonon compensation mechanism. Instead, the experimental energy gap dependences can be quantitatively described by the dephasing mechanism. Temperature dependences of resonant and nonresonant energy transfer rates in the melts are also consistent with the prediction of the dephasing mechanism. The series of results suggest that the dephasing mechanism can be dominant not only in solutions, but also in melts (pure liquids without solvents), only if the molecular motions (translations and rotations) are much faster than the nonresonant energy transfer processes. |
| |
| Keywords: | Vibrational energy transfers 2D IR Phonon compensation mechanism Dephasing mechanism |
|
| 点击此处可从《化学物理学报》浏览原始摘要信息 |
|
点击此处可从《化学物理学报》下载全文 |
|
