Rydberg states photodissociation dynamics

Electronic states and photodissociation dynamics of chloromethyl radical have been studied recently.114-117 Because of the chlorine substitution, there are several low-lying valence excited states (such as l2Ai and 22Bi, which mainly involve the orbitals on the CC1 bond) in addition to the 3s Rydberg state (22Ai), and more dissociation channels are available. 

The fragment excited-state NO(A2S+) is a molecular 3r Rydberg state, and we shall refer to this as NO(A, 3s). The observed NO(A, 3.v) product state distributions supported the notion of a planar dissociation involving restricted intramolecular vibrational energy redistribution (IVR) [176]. A scheme for studying NO dimer photodissociation dynamics via TRPES is depicted in Fig. 25. The NO(A, 3.v) + NO(X) product elimination channel, its scalar and vector properties, and its evolution on the femtosecond time scale have been discussed in a number of recent publications (see Ref. [175] and references cited therein). 

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