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Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy
Author(s) -
Sotome Hikaru,
Okajima Hajime,
Nagasaka Tatsuhiro,
Tachii Yuka,
Sakamoto Akira,
Kobatake Seiya,
Irie Masahiro,
Miyasaka Hiroshi
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000315
Subject(s) - diarylethene , excited state , chemistry , spectroscopy , photochemistry , ring (chemistry) , infrared spectroscopy , infrared , relaxation (psychology) , derivative (finance) , population , molecular physics , atomic physics , photochromism , optics , physics , psychology , social psychology , demography , organic chemistry , quantum mechanics , economics , sociology , financial economics
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.