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Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy.
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-06-22 , DOI: 10.1002/cphc.202000315 Hikaru Sotome 1 , Hajime Okajima 2 , Tatsuhiro Nagasaka 1 , Yuka Tachii 1 , Akira Sakamoto 2 , Seiya Kobatake 3 , Masahiro Irie 4 , Hiroshi Miyasaka 1
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-06-22 , DOI: 10.1002/cphc.202000315 Hikaru Sotome 1 , Hajime Okajima 2 , Tatsuhiro Nagasaka 1 , Yuka Tachii 1 , Akira Sakamoto 2 , Seiya Kobatake 3 , Masahiro Irie 4 , Hiroshi Miyasaka 1
Affiliation
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The geometrical evolution of the reactant and formation of the photoproduct in the cycloreversion reaction of a diarylethene derivative were probed using time‐resolved absorption spectroscopies in the visible to near‐infrared and mid‐infrared regions. The time‐domain vibrational data in the visible region show that the initially formed Franck‐Condon state is geometrically relaxed into the minimum in the excited state potential energy surface, concomitantly with the low‐frequency coherent vibrations. Theoretical calculations indicate that the nuclear displacement in this coherent vibration is nearly parallel to that in the geometrical relaxation. Time‐resolved mid‐infrared spectroscopy directly detected the formation of the open‐ring isomer with the same time constant as the decrease of the closed‐ring isomer in the excited state minimum. This observation reveals that no detectable intermediate, in which the population is accumulated, is present between the excited closed‐ring isomer and the open‐ring isomer in the ground state.
中文翻译：
振动光谱法研究的二芳基乙烯衍生物的回旋反应中光产物的几何演化和形成。
在可见到近红外和中红外区域中，使用时间分辨吸收光谱法研究了二芳基乙烯衍生物的环还原反应中反应物的几何演变和光产物的形成。可见区域中的时域振动数据表明，最初形成的弗兰克-康登态在几何形状上在激发态势能表面上被弛豫到最小，并伴随着低频相干振动。理论计算表明，这种相干振动中的核位移与几何弛豫中的核位移几乎平行。时间分辨的中红外光谱法直接检测到开环异构体的形成，其时间常数与在激发态最小值时闭环异构体的减少相同。
更新日期：2020-06-22
中文翻译：
振动光谱法研究的二芳基乙烯衍生物的回旋反应中光产物的几何演化和形成。
在可见到近红外和中红外区域中，使用时间分辨吸收光谱法研究了二芳基乙烯衍生物的环还原反应中反应物的几何演变和光产物的形成。可见区域中的时域振动数据表明，最初形成的弗兰克-康登态在几何形状上在激发态势能表面上被弛豫到最小，并伴随着低频相干振动。理论计算表明，这种相干振动中的核位移与几何弛豫中的核位移几乎平行。时间分辨的中红外光谱法直接检测到开环异构体的形成，其时间常数与在激发态最小值时闭环异构体的减少相同。
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