Theoretical study on the photochromic cycloreversion reactions of dithienylethenes; on the role of the conical intersections

Journal of the American Chemical Society

Volumn 126, Issue 38, 2004, Pages 12112-12120

  Asano, Yukako ^a   Murakami, Akinori ^b   Kobayashi, Takao ^b   Goldberg, Alexander ^b   Guillaumont, Dominique ^b   Yabushita, Satoshi ^a   Irie, Masahiro ^c   Nakamura, Shinichiro ^b  

^a KEIO UNIVERSITY   (Japan)

^b MITSUBISHI CHEMICAL CORPORATION   (Japan)

^c KYUSHU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL REACTIONS; MOLECULAR VIBRATIONS; PHOTOCHROMISM;

CONICAL INTERACTIONS (CIS); DITHIENYLETHENES; INTERMOLECULAR VIBRATIONAL ENERGY REDISTRIBUTION (IVR); PHOTOCHROMIC CYCLOREVERSIONS;

ETHYLENE;

DITHIENYLETHENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION KINETICS; ENERGY; EQUILIBRIUM CONSTANT; MOLECULAR MODEL; PHOTOACTIVATION; PHOTOCHROMIC CYCLOREVERSION REACTION; PHOTOCHROMISM; REACTION ANALYSIS; THEORETICAL MODEL; VIBRATION;

EID: 4644250742     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja035035o     Document Type: Article

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47. If the feature of the PES, no TS on the 2A surface, at the preliminary nonoptimized CASPT2 level is correct, the reason for the small QYs of the cycloreversion relative to the cyclization reaction, and the temperature dependency of the former reaction, might be attributed to other unknown mechanisms such as the difference of microscopic density of state between the 2A/1A CI (C) and 2A/1A CI (O), or the existence of some vibrational promoting modes on the 2A surface. Such detailed studies are important future subjects for experiments and theory.