Photochemical Reaction Mechanism of Intramolecular H Transfer Reaction of H2 C3 O+ ⋅ Radical Cation

Abstract

The photochemical reaction mechanism underlying the intramolecular H-transfer of the H₂ C₃ O⁺ ⋅ radical cation to the H₂ CCCO⁺ ⋅ methylene ketene cation was elucidated using time-dependent density functional theory and high-level ab initio methods. Once the D₁ state of H₂ C₃ O⁺ ⋅ is populated, the reaction proceeds to form an intermediate (IM) in the D₁ state (IM4_D1 ). The molecular structure of the conical intersection (CI) was optimized using a multiconfigurational ab initio method. The CI is readily accessible because it lies slightly above the IM4_D1 in energy. In addition, the gradient difference vector of the CI is almost parallel to the intramolecular H-transfer reaction coordinate. Once the vibration mode of IM4_D1 which is parallel to the reaction coordinate is populated, the degeneracy of the CI is readily lifted and H₂ CCCO⁺ ⋅ was formed via a relaxation pathway in the D₀ state. Our calculated results clearly describe the photochemical intramolecular H transfer reaction reported in a recent study.

Keywords: ab initio calculations; conical intersection; intramolecular hydrogen transfer; photoisomerization; radical cation.