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arXiv · 0903.0847

Quantum-Classical Liouville Dynamics in the Mapping Basis

Hyojoon Kim·Ali Nassimi·Raymond Kapral
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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, provide 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.

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Hyojoon Kim, Ali Nassimi, Raymond Kapral. 2009-03-04. Quantum-Classical Liouville Dynamics in the Mapping Basis. https://doi.org/10.1063/1.2971041

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