The photodissociation dynamics of CF3NO are modeled by three-dimensional classical trajectory calculations on the S-0 and T-1 electronic potential surfaces that include all vibrational and rotational degrees of freedom. The intramolecular potential energy, surface for CF3NO was obtained by optimizing parameters in an analytical potential function to best fit spectroscopic data and the results of UMP2/6-31 + GX* level ab initio calculations. Initial parent molecule energy and angular momentum distributions are computed using a new method that simulates the conditions of molecular beam experiments. The calculations are directed at interpreting experimental measurements of correlated NO product state distributions in the photodissociation of the nitrosoalkanes. The results show that the v-j correlation of NO photofragment is primarily determined by the C-N-O bending force constant and exit channel barrier on the T-1 surface. (C) 1997 American Institute of Physics.