Scaling behavior of electronic excitations in assemblies of molecules with degenerate ground states

Abstract

The behavior of long space-time excitations in many-electron systems with ground state degeneracy is explored via multiscale analysis. The analysis starts with an ansatz for the wave function's dual dependence on the N-electron configuration (i.e., both by direct means and by indirect means via a set of order parameters). It is shown that a Dirac-like equation form of the wave equation emerges in the limit where the ratio ε (of the average nearest-neighbor distance to the characteristic length of the long-scale phenomenon of interest) is small. Examples of the long scale are the size of a quantum dot, nanotube, or wavelength of a density disturbance. The velocities in the Dirac-like equation are the transition moments of the single-particle momentum operator connecting degenerate ground states. While detailed band structure and the independent quasi-particle picture could underlie the behavior of some systems (as commonly suggested for graphene), the present scaling law results show it is not necessarily the only explanation. Rather, it can follow from the scaling properties of low-lying, long spatial scale excitations and ground state degeneracy, even in strongly interacting systems. The generality of our findings suggests graphene may be just one of many examples of Dirac-like equation behavior. A preliminary validation of our quantum scaling law for molecular arrays is presented. As our scaling law constitutes a coarse-grained wave equation, path integral or other methods derived from it hold great promise for calibration-free, long-time simulation of many-particle quantum systems. © 2010 American Chemical Society.