Long-lived coherence in pentafluorobenzene as a probe of pi pi* - pi sigma* vibronic coupling

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	*Long-lived coherence in pentafluorobenzene as a probe of pi pi - pi sigma* vibronic coupling**
	Hueter, O.1; Sala, M.1; Neumann, H.1,2; Zhang, S.1,3; Studzinski, H.1,4; Egorova, D.1; Temps, F.1
刊名	JOURNAL OF CHEMICAL PHYSICS
	2016-07-07
卷号	145 期号:1
英文摘要	The dynamics of pentafluorobenzene after femtosecond laser excitation to the optically bright pi pi* first excited electronic state have been investigated by femtosecond time-resolved time-of-flight mass spectrometry and femtosecond time-resolved photoelectron imaging spectroscopy. The observed temporal profiles exhibit a bi-exponential decay behavior with a superimposed, long-lived, large-amplitude oscillation with a frequency of nu(osc) = 78-74 cm(-1) and a damping time of tau(D) = 5-2 ps. On the basis of electronic structure and quantum dynamics calculations, the oscillations have been shown to arise due to vibronic coupling between the optically bright pi pi* state and the energetically close-lying optically dark pi sigma* state. The coupling leads to a pronounced double-well character of the lowest excited adiabatic potential energy surface along several out-of-plane modes of b(1) symmetry. The optical electronic excitation initiates periodic wavepacket motion along these modes. In the out-of-plane distorted molecular configuration, the excited state acquires substantial pi sigma* character, thus modulating the ionization probability. The photoelectron spectra and the anisotropy of their angular distribution confirm the periodically changing electronic character. The ionizing probe laser pulse directly maps the coupled electron-nuclear motion into the observed signal oscillations. Published by AIP Publishing.
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
研究领域[WOS]	Chemistry ; Physics
关键词[WOS]	RESOLVED PHOTOELECTRON-SPECTROSCOPY ; THE-IDENTITY APPROXIMATION ; PLESSET PERTURBATION-THEORY ; EXCITED SINGLET-STATES ; ZETA VALENCE QUALITY ; BASIS-SETS ; ELECTRONIC-STRUCTURE ; AROMATIC-MOLECULES ; CLUSTER MODEL ; AB-INITIO
收录类别	SCI
语种	英语
WOS记录号	WOS:000379584700013
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/9447]
专题	武汉物理与数学研究所_数学物理与应用研究部
作者单位	1.Univ Kiel, Inst Phys Chem, Olshausenstr 40, D-24098 Kiel, Germany 2.Univ Kiel, Inst Mat Sci, Kaiserstr 2, D-24143 Kiel, Germany 3.Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan 430071, Peoples R China 4.Bosch Transmiss Technol BV, Dr Hub van Coorneweg 120, NL-5026 RA Tilburg, Netherlands
推荐引用方式 GB/T 7714	Hueter, O.,Sala, M.,Neumann, H.,et al. Long-lived coherence in pentafluorobenzene as a probe of pi pi* - pi sigma* vibronic coupling[J]. JOURNAL OF CHEMICAL PHYSICS,2016,145(1).
APA	Hueter, O..,Sala, M..,Neumann, H..,Zhang, S..,Studzinski, H..,...&Temps, F..(2016).Long-lived coherence in pentafluorobenzene as a probe of pi pi* - pi sigma* vibronic coupling.JOURNAL OF CHEMICAL PHYSICS,145(1).
MLA	Hueter, O.,et al."Long-lived coherence in pentafluorobenzene as a probe of pi pi* - pi sigma* vibronic coupling".JOURNAL OF CHEMICAL PHYSICS 145.1(2016).