WFU Chemistry, Mathematics, and Physics Colloquium

TITLE: Using the Initial Value Representation of Semiclassical Theory to Add Quantum Effects to Classical Molecular Dynamics Simulations

SPEAKER: Professor William H. Miller ,

TIME: Wednesday September 22, 2010 at 4:00 PM

PLACE: Room 111 Carswell Hall*

*Note the unusual location

Semiclassical (SC) theory provides a good description of essentially all quantum effects (interference/coherence, tunneling and other classically forbidden processes, symmetry effects of identical particles, quantization of bounded motion, etc.) in molecular dynamics; this has long been appreciated and validated by many applications to small molecular systems [cf. Adv. Chem. Phys. 25, 69-177 (1974)]. Since SC theory is built on the classical trajectories of the dynamical system, it should in principle be possible to use it also to add quantum effects to classical molecular dynamics simulations of complex molecular systems (i.e., those with many degrees of freedom), e.g., chemical reactions in solution, in clusters, in bio-molecular or any complex environment. The practical implementation of SC theory for systems with many degrees of freedom is based on various initial value representations (IVRs), which have recently undergone a re-birth of interest in this regard. This talk reviews the basic idea of the SC-IVR approach and describes a variety of recent applications that have been carried out using it. For some recent more detailed overviews, see J. Phys. Chem. A 105, 2942-2955 (2001); Proc. Nat. Acad. Sci. 102, 6660-6664 (2005); J. Chem. Phys. 125, 132305.1-8 (2006), J. Phys. Chem. A 113, 1405 (2009).