title: Investigation of the dynamics of two coupled oscillators with mixed quantum-classical methods.
abstract: The dynamics of two coupled oscillators can become quite complex if anharmonic potential energy functions are employed. This type of system therefore represents a good model for an investigation of the performance of mixed quantum-classical methods. In this work, the motion of two coupled particles with a mass ratio of one to ten is studied with three different mixed quantum-classical methods in the presence of anharmonic potential terms for a comparison with exact quantum mechanical calculations. The mixed quantum-classical approaches include the multitrajectory Ehrenfest, the mixed quantum-classical Bohmian (MQCB), and the so-called coupled Schrödinger equations (CSE) formalisms. The analysis shows that while the description of a weakly anharmonic system by the Ehrenfest and MQCB schemes is accurate if proper sampling techniques are applied, both approximations break down rapidly if the anharmonic terms are increased. The performance of the simple CSE prescription, which corresponds to a reduction of the full two-dimensional wave function to two one-dimensional wave functions representing two quantum oscillators coupled via the potential energy in a classical fashion, decreases if the width of the initial wave packet is enlarged. The dependence of the CSE method on the diffuseness of the initial wave packet is therefore opposite to that of the MQCB method, which is more accurate for wide wave packets. Overall, the multitrajectory Ehrenfest ansatz is found to be most successful in reproducing the exact quantum results.
authors.affiliation: Theoretical Chemistry, Department of Chemistry, Technical University Munich, D-85747 Garching, Germany. jingrui.li@ch.tum.de
authors.forename: Jingrui
authors.initials: J
authors.lastname: Li
authors.forename: Clemens
authors.initials: C
authors.lastname: Woywod
authors.forename: Valérie
authors.initials: V
authors.lastname: Vallet
authors.forename: Christoph
authors.initials: C
authors.lastname: Meier
mesh_terms: D000465:Algorithms; D001696:Biomechanical Phenomena; D004735:Energy Transfer; D011789:Quantum Theory; D013057:Spectrum Analysis; D013816:Thermodynamics; D013997:Time Factors