The photodissociation dynamics of state selected OD radicals has been examined at 243 and 226 nm using velocity map imaging to probe the angle-speed distributions of the D(S-2) and O(P-3(2)) products. Both experiment and complementary first principle calculations demonstrate that photodissociation occurs by promotion of OD from high vibrational levels of the ground X (2)Pi state to the repulsive 1 (2)Sigma(-) state. (C) 2003 American Institute of Physics.