We propose a novel scheme for monitoring the transition between deflagration and detonation-like behavior of small-scale explosive samples-in-vacuum subjected to short duration shock stimuli. Our approach relies on measuring the chemical identities and velocity distributions of the gaseous species produced by such samples; e.g. the relatively low velocity expansion-quenched reaction intermediates produced by deflagration versus the hyperthermal thermodynamically stable molecules generated by the termination of a detonation wave at an explosive-vacuum interface. We demonstrate our ability to detect such species by time-of-flight mass spectrometry (TOFMS) using fast Al atoms produced by laser ablation of aluminum metal. Extensive SIMION simulations of ion trajectories in our mass spectrometer lead to a semi-quantitative model connecting the system operating parameters and the velocity-dependent neutral species detection efficiency. We present a method for correcting our data for these detection biases, and for transforming them into neutral species velocity and kinetic energy distributions. We also present preliminary TOFMS data of hyperthermal organic molecular species produced by direct laser ablation/ignition of thin-film nitrocellulose samples.