Femtosecond laser pump-probe techniques are employed to investigate the mechanisms and dynamics of the photodissociation of HMX and RDX from their excited electronic states at three wavelengths (230 nm, 228 nm, and 226 nm). The only observed product is the NO molecule. Parent HMX and RDX ions are not observed. The NO molecule has a resonant A(2)Sigma <- X-2 Pi (0,0) transition at 226 nm and off-resonance two-photon absorption at 228 nm and 230 nm. Pump-probe transients of the NO product at both off-resonance and resonance absorption wavelengths indicate the decomposition dynamics of HMX and RDX falls into the timescale of our laser pulse duration (180 fs). (c) 2006 Published by Elsevier B.V.