Quantum dynamical simulations based on ab initio potentials show that a single linearly polarized laser pulse (infrared or ultraviolet) can selectively excite one enantiomer from a racemic mixture. The degeneracy of the chiral pair is broken and a sequential reaction can distinguish between the two enantiomers based on energetic criteria. For instance, the undesired enantiomer can be photodestructed and the products can be probed using mass spectroscopy. The proposed scheme is applied to H2POSD, which has a low interconversion barrier and to a chiral olefin possessing stable enantiomers. (C) 2003 Elsevier Science B.V. All rights reserved.