Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S-2 state

doi:10.1063/1.4959131

	Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S-2 state
	Zhou, Pan-Wang1 ; Zhao, Li 1,2; Zhao, Guang-Jiu 1
刊名	JOURNAL OF CHEMICAL PHYSICS
	2016-07-28
卷号	145 期号:4
ISSN号	0021-9606
DOI	10.1063/1.4959131
文献子类	Article
英文摘要	The trans-urocanic acid, a UV chromophore in the epidermis of human skin, was found to exhibit a wavelength dependent isomerization property. The isomerization quantum yield to cis-urocanic is greatest when being excited to the S-1 state, whereas exciting the molecule to the S-2 state causes almost no isomerization. The comparative photochemical behavior of the trans-urocanic on the S-1 and S-2 states continues to be the subject of intense research effort. This study is concerned with the unique photo-behavior of this interesting molecule on the S-2 state. Combining the on-the-fly surface hopping dynamics simulations and static electronic structure calculations, three decay channels were observed following excitation to the S-2 state. An overwhelming majority of the molecules decay to the S-1 state through a planar or pucker characterized minimum energy conical intersection (MECI), and then decay to the ground state along a relaxation coordinate driven by a pucker deformation of the ring. A very small fraction of molecules decay to the S-1 state by a MECI characterized by a twisting motion around the CC double bond, which continues to drive the molecule to deactivate to the ground state. The latter channel is related with the photoisomerization process, whereas the former one will only generate the original trans-form products. The present work provides a novel S-2 state decay mechanism of this molecule, which offers useful information to explain the wavelength dependent isomerization behavior. Published by AIP Publishing.
WOS关键词	SURFACE HOPPING METHOD ; ZHU-NAKAMURA THEORY ; EXCITED-STATES ; PHOTOISOMERIZATION ; PHOTOCHEMISTRY ; PHOTOBIOLOGY ; OXYGEN
WOS研究方向	Chemistry ; Physics
语种	英语
出版者	AMER INST PHYSICS
WOS记录号	WOS:000381679800031
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/170004]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Zhou, Pan-Wang; Zhao, Guang-Jiu
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Zhou, Pan-Wang,Zhao, Li,Zhao, Guang-Jiu. Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S-2 state[J]. JOURNAL OF CHEMICAL PHYSICS,2016,145(4).
APA	Zhou, Pan-Wang,Zhao, Li,&Zhao, Guang-Jiu.(2016).Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S-2 state.JOURNAL OF CHEMICAL PHYSICS,145(4).
MLA	Zhou, Pan-Wang,et al."Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S-2 state".JOURNAL OF CHEMICAL PHYSICS 145.4(2016).