ABSTRACT:The branching ratios for the spin-forbidden photodissociation channels of 12 C 16 O in the vacuum ultraviolet (VUV) photon energy region from 102 500 (12.709 eV) to 106 300 cm −1 (13.180 eV) have been investigated using the VUV laser time-slice velocity-map imaging photoion technique. The excitations to three 1 Σ + and six 1 Π Rydberg-type states, including the progression of W(3sσ) 1 Π(v′ = 0, 1, and 2) vibrational levels of CO, have been identified and investigated. The branching ratios for the product channels C( 3 P) + O( 3 P), C( 1 D) + O( 3 P), and C( 3 P) + O( 1 D) of these predissociative states are found to depend on the electronic, vibrational, and rotational states of CO being excited. Rotation and e/f-symmetry dependences of the branching ratios into the spin-forbidden channels have been confirmed for several of the 1 Π states, which can be explained using the heterogeneous interaction with the repulsive D′ 1 Σ + state. The percentage of the photodissociation into the spin-forbidden channels is found to increase with increasing the rotational quantum number for the K(4pσ) 1 Σ + (v′ = 0) state. This has been rationalized using a 1 Σ + to 1 Π to 3 Π coupling scheme, where the final 3 Π state is a repulsive valence state correlating to the spin-forbidden channel.