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Excited State Intramolecular Proton Transfer of 1-Hydroxyanthraquinone
Si-mei Sun,Song Zhang*,Kai Liu,Ya-ping Wang,Miao-miao Zhou,Bing Zhang
Author NameAffiliationE-mail
Si-mei Sun State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China  
Song Zhang* State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China zhangsong@wipm.ac.cn 
Kai Liu State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China  
Ya-ping Wang State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China  
Miao-miao Zhou State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China  
Bing Zhang State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China bzhang@wipm.ac.cn 
Abstract:
The excited state intra-molecular proton transfer dynamics of 1-hydroxyanthraquinone in solution are investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. Two characteristic bands of excited state absorption and stimu-lated emission are observed in transient absorption spectra with the excitation by the pump wavelength of 400 nm. From the delayed stimulated emission signal, the time scale of the intra-molecular proton transfer is determined to be about 32 fs. The quantum chemistry calculations show that the molecular orbits and the order of the S2 and S1 states are rever-sal and a conical intersection is demonstrated to exist along the proton transfer coordinate. After proton transfer, the second excited state of tautomer populated via the conical intersection undergoes the internal conversion with ~200 fs and the following intermolecular energy relaxation with ~16 ps. The longer component 300 ps can be explained in terms of the relaxation from excited-state tautomer to its ground state. From our observations, two proton transfer pathways via a conical intersection are proposed and the dominated one preserves the molecular orbits.
Key words:  Proton transfer, Conical intersection, Transient absorption spectroscopy, 1-Hydroxyanthraquinone
FundProject:
1-羟基蒽醌的分子内质子转移动力学
孙四梅,张嵩*,刘凯,王雅萍,周淼淼,张冰*
摘要:
利用飞秒瞬态吸收光谱结合量化计算研究了1-羟基蒽醌在溶剂中的激发态分子内质子转移动力学. 分子受到400 nm光激发后的瞬态吸收谱呈现出激发态吸收和受激辐射两个光谱带. 受激辐射信号较激发态吸收信号滞后出现,由此确定质子转移时间是32 fs. 量化计算表明分子在沿质子转移路径衰变时,分子轨道和能级次序发生了反转,形成锥形交叉. 在质子转移之后,经锥形交叉布居的电子态发生内转换和分子间能量弛豫,时间分别是200 fs和16 ps. 基态回复时间是300 ps. 通过实验和理论研究,证实存在两个质子转移路径,其中主要的衰变路径保持了原来轨道的性质.
关键词:  质子转移,锥形交叉,飞秒瞬态吸收光谱,1-羟基蒽醌
DOI:10.1063/1674-0068/28/cjcp1504078
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