An eulerian surface hopping method for the schrödinger equation with conical crossings

Abstract

In a nucleonic propagation through conical crossings of electronic energy levels, the codimension two conical crossings are the simplest energy level crossings, which affect the Born- Oppenheimer approximation in the zeroth order term. The purpose of this paper is to develop the surface hopping method for the Schrödinger equation with conical crossings in the Eulerian formulation. The approach is based on the semiclassical approximation governed by the Liouville equations, which are valid away from the conical crossing manifold. At the crossing manifold, electrons hop to another energy level with the probability determined by the Landau-Zener formula. This hopping mechanics is formulated as an interface condition, which is then built into the numerical flux for solving the underlying Liouville equation for each energy level. While a Lagrangian particle method requires the increase in time of the particle numbers, or a large number of statistical samples in a Monte Carlo setting, the advantage of an Eulerian method is that it relies on fixed number of partial differential equations with a uniform in time computational accuracy. We prove the positivity and l1-stability and illustrate by several numerical examples the validity and accuracy of the proposed method. © 2011 Society for Industrial and Applied Mathematics.