Quantum-classical Liouville dynamics in the mapping basis

URL:

https://www.scopus.com/inward/record.uri?eid=2-s2.0-50849119690&doi=10.1063%2f1.2971041&partnerID=40&md5=d313fc04e5f4e9382d9a0044cd03b02a

Keywords:

algorithm, Algorithms, Article, Chemical, chemical model, chemistry, Computer networks, Computer Simulation, electron, Electrons, Equations of motion, Evolution equations, Large scale systems, Liouville equations, methodology, Models, Oscillometry, Physical, physical chemistry, Quantum Theory, Quantum-classical, Statistical, statistical model, Theoretical, theoretical model

Abstract:

The quantum-classical Liouville equation describes the dynamics of a quantum subsystem coupled to a classical environment. It has been simulated using various methods, notably, surface-hopping schemes. A representation of this equation in the mapping Hamiltonian basis for the quantum subsystem is derived. The resulting equation of motion, in conjunction with expressions for quantum expectation values in the mapping basis, provides another route to the computation of the nonadiabatic dynamics of observables that does not involve surface-hopping dynamics. The quantum-classical Liouville equation is exact for the spin-boson system. This well-known model is simulated using an approximation to the evolution equation in the mapping basis, and close agreement with exact quantum results is found. © 2008 American Institute of Physics.