Including quantum effects in the dynamics of complex (i.e., large) molecular systems.
The development in the 1950s and 1960s of crossed molecular beam methods for studying chemical reactions at the single-collision molecular level stimulated the need and desire for theoretical methods to describe these and other dynamical processes in molecular systems. Chemical dynamics theory has made great strides in the ensuing decades, so that methods are now available for treating the quantum dynamics of small molecular systems essentially completely. For the large molecular systems that are of so much interest nowadays (e.g., chemical reactions in solution, in clusters, in nanostructures, in biological systems, etc.), however, the only generally available theoretical approach is classical molecular dynamics (MD) simulations. Much effort is currently being devoted to the development of approaches for describing the quantum dynamics of these complex systems. This paper reviews some of these approaches, especially the use of semiclassical approximations for adding quantum effects to classical MD simulations, also showing some new versions that should make these semiclassical approaches even more practical and accurate.
Miller
William H
WH
Department of Chemistry and K. S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720-1460, USA. millerwh@berkeley.edu