The Journal of Chemical Physics · 1982 · 491 citations · 8 references
Natural SciencesPhysicsComputational PhysicsMolecular PhysicsQuantum MechanicsComputational Quantum MechanicsDensity Matrix FormalismMonte Carlo MethodsMonte Carlo SimulationPath Integral FormulationSimulation MethodsDensity MatrixDensity Matrix FormulationDiscrete Space RepresentationHarmonic Oscillator ApproximationHarmonic Oscillator Wave FunctionsPath Integral ApproximationPath Integral Monte CarloVirial Theorem
A Monte Carlo procedure based on a discrete point representation of the path integral for the density matrix is explored. It is found that the variance of the estimator used to evaluate the energy grows as the square root of the number of discrete points used, and is therefore to be avoided in highly quantum mechanical systems, where the number of discrete points must be large. A new energy estimator based on the virial theorem is proposed and shown to be well behaved. The main points of the paper are illustrated, using the harmonic oscillator as an example.
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