MRMP study of radical photodissociation reaction thresholds for acetaldehyde and acetone

Abstract

Energies between the S 1 origin and barrier top for acetaldehyde and acetone radical photodissociation reactions were calculated using the multireference Møller–Plesset method and compared with experimental values derived from fluorescence decay rate changes. The radical photodissociation reaction thresholds for acetaldehyde and acetone were calculated to be 1770 cm −1 and 2230 cm −1 above the S 1 origin, respectively, when TZV(2df,2p) basis sets were used. The calculated values agree with the energies at which the fluorescence decay rates begin to increase.