The technique of velocity‐aligned Doppler spectrosocopy (VADS) is presented and discussed. For photolysis/probe experiments with pulsed initiation, VADS can yield Doppler profiles for nascent photofragments that allow detailed center‐of‐mass (c.m.) kinetic energy distributions to be extracted. When compared with traditional forms of Doppler spectroscopy, the improvement in kinetic energy resolution is dramatic. Changes in the measured profiles are a consequence of spatial discrimination (i.e., focused and overlapping photolysis and probe beams) and delayed observation. These factors result in the selective detection of species whose velocities are aligned with the wave vector of the probe radiationkpr, thus revealing the speed distribution alongkprrather than the distribution of nascent velocity components projected upon this direction. Mathematical details of the procedure used to model VADS are given, and experimental illustrations for HI, H2S, and NH3photodissociation are presented. In these examples, pulsed photodissociation produces H atoms that are detected by sequential two‐photon, two‐frequency ionization via Lyman‐&agr; with a pulsed laser (121.6+364.7 nm), and measuring the Lyman‐&agr; Doppler profile as a function of probe delay reveals both internal and c.m. kinetic energy distributions for the photofragments. Strengths and weaknesses of VADS as a tool for investigating photofragmentation phenomena are also discussed.
展开▼