Theoretical Investigation of the Reaction Mechanism of the Photoisomerization of 1,2‐Dihydro‐1,2‐azaborine |
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| Authors: | Prof Dr Joonghan Kim Jiwon Moon Dr Jeong Sik Lim |
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| Affiliation: | 1. Department of Chemistry, The Catholic University of Korea, Bucheon, 420‐743 (Republic of Korea);2. Division of Metrology for Quality Life, Korea Research Institute of Standards and Science (KRISS), Daejeon (Republic of Korea) |
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| Abstract: | 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 S0 and S1 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→TS1→CI→IM0→TS0P→product. The product was not directly formed through the CI, and the IM0 existed on the S0 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. |
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| Keywords: | conical intersections multireference character photoisomerization reaction mechanisms thermal reactions |
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