Model study on the pyridine-Dewar pyridine and some related photoisomerization reactions.
The potential energy surfaces corresponding to the photochemical reactions of pyridine, phosphinine, and arsabenzene have been investigated by employing the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. The thermal (or dark) reactions of these reactant species have also been examined using the same level of theory. The mechanisms of drastic structural change in the excited- and ground-state reactions of pyridine, phosphinine, and arsabenzene and the differences between them are elucidated. The theoretical investigations suggest that conical intersections play a crucial role in their photoisomerization reactions. The results obtained allow a number of predictions to be made.
Su
Ming-Der
MD
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan. midesu@mail.ncyu.edu.tw
D001152:Arsenicals / Q000737:chemistry* / Q000528:radiation effects; D001555:Benzene Derivatives / Q000737:chemistry* / Q000528:radiation effects; D007536:Isomerism; D008027:Light; D008956:Models, Chemical; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry* / Q000528:radiation effects; D010777:Photochemistry; D011725:Pyridines / Q000737:chemistry* / Q000528:radiation effects; D013499:Surface Properties
D001152:Arsenicals; D001555:Benzene Derivatives; D009943:Organophosphorus Compounds; D011725:Pyridines; C519089:arsabenzene; C519090:phosphinine; C023666:pyridine