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学科主题物理化学
Hydrogen bonding effects on the photochemistry of chromophores
Zhao GJ(赵广久); Han KL(韩克利)
会议名称2010 International Chemical Congress of Pacific Basin Societies:Theory of Excited States Structures and Dynamics :Application to Organic Materials and Biosystems
会议日期2010-12-15
2010-12-15
会议地点美国
其他题名发色团光化学的氢键效应
页码154/2
部门归属十一室
主办者美国化学会,加拿大化学会、日本化学会、新西兰化学会、澳大利亚皇家化学会,韩国化学会, 中国化学会
英文摘要Intermolecular hydrogen bonding, as a site-specific interaction between hydrogen donor and acceptor molecules, is a very important type of solute-solvent interactions. It is central to the understanding of microscopic structure and function in many molecular systems, such as hydrogen-bonded water or alcohols networks, chromophores, proteins, and DNA building blocks of the life. Furthermore, it also plays an important role on the photochemistry of the hydrogen-bonded systems in their electronically excited states. In this talk, we have reviewed our recent investigations about the hydrogen bonding effects on the photochemistry of chromophores in solution. The electronically excited states of chromophores were theoretically studied using the time-dependent density functional theory (TDDFT) method. At the same time, the infrared spectra in the ground state and electronically excited state of chromophores were also simulated. By monitoring the spectral shifts of some characterized vibrational modes involved in the formation of hydrogen bonds in different electronic states, it has been demonstrated for the first time that the intermolecular hydrogen bonds between chromophores and hydrogen donating solvents are significantly strengthened in the electronically excited state. This hydrogen bonding dynamics of photoexcited chromophores occurs on ultrafast timescales mainly set by vibrational motions of the hydrogen donor and acceptor groups, and it controls the excited-state dynamics of hydrogen-bonded complexes in a significant way. We have demonstrated that the radiationless deactivation via internal conversion (IC) from the fluorescent state to the ground state can be enhanced by the hydrogen bond strengthening in the excited state. The solute-solvent intermolecular photoinduced electron transfer (ET) reaction, which is facilitated by the hydrogen bond strengthening, has been proposed to account for the drastic fluorescence quenching behaviors of chromophores in alcoholic solvents. Moreover, the site-specific solvation dynamics can also be induced by the hydrogen bond strengthening in the electronically excited state.
语种中文
文献类型会议论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/114450
专题中国科学院大连化学物理研究所
通讯作者Han KL(韩克利)
推荐引用方式
GB/T 7714
Zhao GJ,Han KL. Hydrogen bonding effects on the photochemistry of chromophores[C],2010:154/2.
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