Premium
Theoretical Investigation of the Reaction Mechanism of the Photoisomerization of 1,2‐Dihydro‐1,2‐azaborine
Author(s) -
Kim Joonghan,
Moon Jiwon,
Lim Jeong Sik
Publication year - 2015
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.201500153
Subject(s) - photoisomerization , isomerization , complete active space , chemistry , ab initio , conical intersection , transition state , multireference configuration interaction , computational chemistry , density functional theory , reaction mechanism , photochemistry , basis set , catalysis , molecule , organic chemistry
The photoisomerization of 1,2‐dihydro‐1,2‐azaborine was investigated by high‐level multireference ab initio and density functional theory calculations. The intermediates (IMs) and transition states (TSs) on the S 0 and S 1 states were optimized using the state‐averaged complete active space self‐consistent field method. The multireference configuration interaction method with the Davidson correction was used to obtain accurate energetics. Moreover, the conical intersections (CIs), which play a crucial role in photoisomerization, were also optimized. On the basis of the calculation results, the most favorable proposed reaction pathway is as follows: reactant→Franck‐Condon region→TS 1 →CI→IM 0 →TS 0P →product. The product was not directly formed through the CI, and the IM 0 existed on the S 0 state. These results show that the isomerization of 1,2‐dihydro‐1,2‐azaborine involves both photoreactions and thermal reactions. The calculated results clarify recent experimental observations.