A CASPT2//CASSCF study of the quartet excited state $$\tilde{a}^{4}A^{\prime\prime}$$ of the HCNN radical

Abstract

Complete active space self-consistent field and second-order multiconfigurational perturbation theory methods have been performed to investigate the quartet excited state \({\tilde{a}}^{4}{A^{\prime\prime}}\) potential energy surface of HCNN radical. Two located minima with respective cis and trans structures could easily dissociate to CH \(({\tilde{a}}^{4}\Sigma^{-})\) and \(N_{2} ({\tilde{X}}^{1}\Sigma_{\rm g}^{+})\) products with similar barrier of about 16.0 kcal/mol. In addition, four minimum energy crossing points on a surface of intersection between \({\tilde{a}}^{4}A^{\prime\prime}\) and X (\(X={\tilde{X}}^{2}A^{\prime\prime}\) and \({\tilde{A}}^{2}A^{\prime}\)) states are located near to the minima. However, the intersystem crossing \({\tilde{a}}^{4}A^{\prime\prime} \rightarrow X\) is weak due to the vanishingly small spin–orbit interactions. It further indicates that the direct dissociation on the \({\tilde{a}}^{4}{A^{\prime\prime}}\) state is more favored. This information combined with the comparison with isoelectronic HCCO provides an indirect support to the recent experimental proposal of photodissociation mechanism of HCNN.