화학공학소재연구정보센터
Journal of Chemical Physics, Vol.100, No.1, 473-480, 1994
On the Perturbation of the (B) over-Tilde2A’ State of Hco by the 1-4A" and 1-4A’ States - Surfaces of Intersection and Spin-Orbit Interactions
The excited B 2A’ state of HCO is studied using multiconfiguration self-consistent field/configuration interaction wave functions of 300 000 to 1 400 000 terms. Equilibrium structures for the X 2A’, B 2A’, 1 4A", and 1 4A’ states are determined as is the X 2A’ - B 2A’ electronic transition dipole moment. This dipole transition moment vector is found to make an angle of approximately + 34-degrees with the inertial a axis of the B 2A’ state. The possibility of spin-orbit induced perturbation of the low-lying vibrational levels of the B 2A’ state attributable to the 1 4A" or 1 4A’ states is considered. The minimum energy points on the surface of intersection of the B 2A’ and 1 4A" states, denoted MECP(B 2A’ - 1 4A"), and of the B 2A’ and 1 4A’ states, denoted MECP (B 2A’ - 1 4A’), are determined. MECP (B 2A’ - 1 4A") is located very close to the 1 4A" equilibrium structure and is only approximately 1500 cm-1 above the B 2A’ minimum. At MECP (B 2A’ -1 4A") the parallel and perpendicular components of the B 2A’ approximately 1 4A" spin-orbit coupling, based on the microscopic Breit-Pauli operator, are approximately 50 and 4 cm-1, respectively. No barrier was found separating the B 2A’ equilibrium structure and MECP(B 2A’ - 4A"). MECP(B 2A - 1 4A’) is close to the 1 4A’ minimum and is placed approximately 2400 cm-1 above the minimum of the B 2A’ state. However, the B 2A’approximately 1 4A’ spin-orbit interaction, a perpendicular interaction, is only approximately 1 cm-1. Additional points on the B 2A’ - 1 4A" surface of intersection and the corresponding B 2A’ approximately 1 4A" spin-orbit interactions are determined.