MRMP STUDY OF RADICAL PHOTODISSOCIATION REACTION THRESHOLDS FOR ACETALDEHYDE AND ACETONE

Energies between the S-1 origin and barrier top for acetaldehyde and a cetone radical photodissociation reactions were calculated using the m ultireference Moller-Plesset method and compared with experimental val ues derived from fluorescence decay rate changes. The radical photodis sociation reaction thresholds for acetaldehyde and acetone were calcul ated to be 1770 cm(-1) and 2230 cm(-1) above the S-1 origin, respectiv ely, when TZV(2df, 2p) basis sets were used. The calculated values agr ee with the energies at which the fluorescence decay rates begin to in crease. (C) 1998 Elsevier Science B.V.