Ab initio potential energy surfaces of charge‐transfer reactions: F++CO→F+CO+

Ab initio potential energy surfaces (PESs) of the charge‐transfer reaction F++CO→F+CO+, studied experimentally by Kusunoki and Ishikawa [J. Chem. Phys. 82, 4991 (1985)], are calculated by the MRSD‐CI method using the DZP basis set. Six low‐lying triplet A’ and six A‘ states, correlated to the initial state F+(3P)+CO(X 1Σ+), the final state F(2P) + CO+(A 2Π) and the ground state F(2P)+CO+ (X 2Σ+ ), are investigated for full three‐dimensional interactions between the F atom and the CO molecule. The mechanism of charge transfer is discussed based on the PES characteristics and the nonadiabatic coupling elements between the initial and relevant final states. A simple theoretical model which emphasizes the importance of the nonadiabatic transition along the CO vibrational coordinate is presented to interpret the vibrational excitation of the product CO+ (A).