Quantum-classical Liouville dynamics in the mapping basis

Journal Article · Thu Aug 28 04:00:00 EDT 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2971041· OSTI ID:21106218

Kim, Hyojoon ^[1]; Nassimi, Ali; Kapral, Raymond ^[2]

---

1. Department of Chemistry, Dong-A University, Hadan-2-dong, Busan 604-714 (Korea, Republic of)
2. Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 (Canada)

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.

• OSTI ID: 21106218
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 129; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
APPROXIMATIONS
BOLTZMANN-VLASOV EQUATION
EQUATIONS OF MOTION
HAMILTONIANS
MAPPING
SIMULATION
SURFACES