Propagators for Quantum-Classical Models: Commutator-Free Magnus Methods

• Published in: Journal of chemical theory and computation 2020-03, Vol.16 (3), p.1420-1430
• Main Authors: Gómez Pueyo, Adrián, Blanes, Sergio, Castro, Alberto
• Format: Article
• Language: English
• Subjects: Algorithms; Commutators; Density functional theory; Electrons; Linear systems; Mathematical models; Molecular dynamics; Nonlinear systems; Numerical methods; Propagation; Schrodinger equation; Time dependence
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.9b01031

We consider the numerical propagation of models that combine both quantum and classical degrees of freedom, usually, electrons and nuclei, respectively. We focus, in our computational examples, on the case in which the quantum electrons are modeled with time-dependent density-functional theory, although the methods discussed below can be used with any other level of theory. Often, for these so-called quantum-classical molecular dynamics models, one uses some propagation technique to deal with the quantum part and a different one for the classical equations. While the resulting procedure may, in principle, be consistent, it can however spoil some of the properties of the methods, such as the accuracy order with respect to the time step or the preservation of the geometrical structure of the equations. Few methods have been developed specifically for hybrid quantum-classical models. We propose using the same method for both the quantum and classical particles, in particular, one family of techniques that proves to be very efficient for the propagation of Schrödinger-like equations: the (quasi)-commutator free Magnus expansions. These have been developed, however, for linear systems, yet our problem is nonlinear: formally, the full quantum-classical system can be rewritten as a nonlinear Schrödinger equation, i.e., one in which the Hamiltonian depends on the system itself. The Magnus expansion algorithms for linear systems require the application of the Hamiltonian at intermediate points in a given propagating interval. For nonlinear systems, this poses a problem as this Hamiltonian is unknown due to its dependence on the state. We approximate it by employing a higher order extrapolation using previous steps as input. The resulting technique can then be regarded as a multistep technique or, alternatively, as a predictor corrector formula.