A simple and efficient evolution operator for time-dependent Hamiltonians: the Taylor expansion

No compact expression of the evolution operator is known when the Hamiltonian operator is time dependent, like when Hamiltonian operators describe, in a semiclassical limit, the interaction of a molecule with an electric field. It is well known that Magnus [N. Magnus, Commun. Pure Appl. Math. 7, 649 (1954)] has derived a formal expression where the evolution operator is expressed as an exponential of an operator defined as a series. In spite of its formal simplicity, it turns out to be difficult to use at high orders. For numerical purposes, approximate methods such as "Runge-Kutta" or "split operator" are often used usually, however, to a small order (< 5), so that only small time steps, about one-tenth or one-hundredth of the field cycle, are acceptable. Moreover, concerning the latter method, split operator, it is only very efficient when a diagonal representation of the kinetic energy operator is known. The Taylor expansion of the evolution operator or the wave function about the initial time provides an alternative approach, which is very simple to implement and, unlike split operator, without restrictions on the Hamiltonian. In addition, relatively large time steps (up to the field cycle) can be used. A two-level model and a propagation of a Gaussian wave packet in a harmonic potential illustrate the efficiency of the Taylor expansion. Finally, the calculation of the time-averaged absorbed energy in fluoroproprene provides a realistic application of our method. (c) 2007 American Institute of Physics.