Femtosecond fluorescence study of the reaction pathways and nature of the reactive S1 state of cis-stilbene

Physical Chemistry Chemical Physics : PCCP
Takumi NakamuraTahei Tahara

Abstract

We report a femtosecond time-resolved fluorescence study of cis-stilbene, a prototypical molecule showing ultrafast olefinic photoisomerization and photocyclization. The time-resolved fluorescence signals were measured in a nonpolar solvent over a wide ultraviolet-visible region with excitation at 270 nm. The time-resolved fluorescence traces exhibit non-single exponential decays which are well fit with bi-exponential functions with time constants of τ(A) = 0.23 ps and τ(B) = 1.2 ps, and they are associated with the fluorescence emitted from different regions of the S(1) potential energy surface (PES) in the course of the structural change. Quantitative analysis revealed that the two fluorescent components exhibit similar intrinsic time-resolved spectra extending from 320 nm to 700 nm with the (fluorescence) oscillator strength of f(A) = 0.32 and f(B) = 0.21, respectively. It was concluded that the first component is assignable to the fluorescence from the untwisted S(1) PES region where the molecule reaches immediately after the initial elongation of the central C[double bond, length as m-dash]C bond, while the second component is the fluorescence from the substantially twisted region around a shallow S(1) potential minimum. T...Continue Reading

References

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Feb 3, 2007·Analytical Chemistry·Noël BoensAtsushi Miura
Apr 26, 2011·Journal of the American Chemical Society·Zhengrong WeiTahei Tahara

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Citations

Nov 2, 2016·The Journal of Physical Chemistry. a·Yu HarabuchiTetsuya Taketsugu
Mar 29, 2019·Physical Chemistry Chemical Physics : PCCP·Jamie D YoungArthur E Bragg
Jan 14, 2014·Journal of Chemical Theory and Computation·Amanda J NeukirchJames P Lewis
Nov 12, 2013·Journal of Chemical Theory and Computation·I N Ioffe, A A Granovsky
May 20, 2020·The Journal of Physical Chemistry. B·Hayley WeirTodd J Martínez
Jun 22, 2018·The Journal of Physical Chemistry. a·Jack Saltiel, Shipra Gupta
Jun 26, 2020·The Journal of Physical Chemistry. a·Jana L van den BergRichard N Zare

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