Semiclassical representations of electronic structure and dynamics.
We use a new formulation of the semiclassical coherent state propagator to derive and evaluate several different approximate representations of electron dynamics. For each representation we examine: (1) its ability to treat quantum effects and electron correlation, (2) its expected scaling with system size, and (3) the types of systems for which it can be used. We also apply two of the methods to a pair of model problems, namely the minimal basis electron dynamics in H2 and the magnetization dynamics in a cluster model of the Kagome lattice, in order to verify the feasibility of these approaches for realistic systems. Based on all these criteria, we find that the representation that takes the electron spins as the classical variables is particularly promising for the quantitative and qualitative description of large systems.
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA. tvan@mit.edu
Troy
T
Van Voorhis
David R
DR
Reichman