Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

doi:10.1063/1.4938423

	Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study
	Wu, Guorong 2,3,4; Neville, Simon P.5; Schalk, Oliver 2,6; Sekikawa, Taro 7; Ashfold, Michael N. R.8; Worth, Graham A.9; Stolow, Albert 1,2,5
刊名	JOURNAL OF CHEMICAL PHYSICS
	2016-01-07
卷号	144 期号:1
ISSN号	0021-9606
DOI	10.1063/1.4938423
文献子类	Article
英文摘要	The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A(2)(pi sigma) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B-1(pi 3p(y)) Rydberg state, followed by prompt internal conversion to the A(2)(pi sigma) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A(2)(pi sigma) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A(2)(pi sigma) state, facilitating wavepacket motion around the potential barrier in the N-CH3 dissociation coordinate. (C) 2016 AIP Publishing LLC.
WOS关键词	NEAR-ULTRAVIOLET PHOTOLYSIS ; PHOTODISSOCIATION DYNAMICS ; UV PHOTODISSOCIATION ; ELECTRONIC STATES ; ATOM ELIMINATION ; PYRROLE ; MOLECULES ; PHOTOCHEMISTRY ; APPROXIMATION ; IONIZATION
WOS研究方向	Chemistry ; Physics
语种	英语
出版者	AMER INST PHYSICS
WOS记录号	WOS:000368617300015
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/171436]
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	Stolow, Albert
作者单位	1.Univ Ottawa, Dept Phys, 150 Louis Pasteur, Ottawa, ON K1N 6N5, Canada 2.Natl Res Council Canada, 100 Sussex Dr, Ottawa, ON K1A 0R6, Canada 3.Chinese Acad Sci, State Key Lab Mol React Dynam, Dalian Inst Chem Phys, Dalian 116023, Liaoning, Peoples R China 4.Univ Sci & Technol China, Synerget Innovat Ctr Quantum Informat & Quantum P, Hefei 230026, Anhui, Peoples R China 5.Univ Ottawa, Dept Chem, 10 Marie Curie, Ottawa, ON K1N 6N5, Canada 6.Stockholm Univ, Dept Phys, AlbaNova Univ Ctr, Roslagstullsbacken 21, S-10691 Stockholm, Sweden 7.Hokkaido Univ, Dept Appl Phys, Kita Ku, Kita 13 Nishi 8, Sapporo, Hokkaido 0608628, Japan 8.Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England 9.Univ Birmingham, Sch Chem, Birmingham B15 2TT, W Midlands, England
推荐引用方式 GB/T 7714	Wu, Guorong,Neville, Simon P.,Schalk, Oliver,et al. Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study[J]. JOURNAL OF CHEMICAL PHYSICS,2016,144(1).
APA	Wu, Guorong.,Neville, Simon P..,Schalk, Oliver.,Sekikawa, Taro.,Ashfold, Michael N. R..,...&Stolow, Albert.(2016).Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study.JOURNAL OF CHEMICAL PHYSICS,144(1).
MLA	Wu, Guorong,et al."Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study".JOURNAL OF CHEMICAL PHYSICS 144.1(2016).