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The Journal of Chemical Physics

Publisher’s Note: “Multiconfigurational system-bath dynamics using Gaussian wave packets: Energy relaxation and decoherence induced by a finite-dimensional bath” [J. Chem. Phys. 119 , 5364 (2003)]

Irène Burghardt, Mathias Nest, Graham A. Worth

Published Mar 29, 2004• 0 citations
Publisher
DOI
10.1063/1.1690245

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A variational approach for the quantum dynamics of statistical mixtures is developed, which is based upon the representation of the natural states of the mixture in terms of hybrid Gaussian-based Multiconfiguration Time-Dependent Hartree (G-MCTDH) wavefunctions. The method, termed ρG-MCTDH, is combined with a treatment of dissipation and decoherence based on the nonstochastic open-system Schrödinger equations. The performance and the convergence properties of the approach are illustrated for a two-dimensional tunneling system, where the primary tunneling coordinate, represented by flexible single-particle functions, is resonantly coupled to a second harmonic mode, represented by Gaussian wave packets. The harmonic coordinate is coupled to the environment and two different processes are studied: (i) vibrational relaxation at zero temperature described by a master equation in the Lindblad form and (ii) thermalization induced by the Caldeira-Leggett master equation. In the second case, the evolution from a quantum tunneling regime to a quasistationary classical-limit distribution, driven by the heat bath, is visualized using a flux analysis.

The Journal of Chemical Physics•Jun 12, 2019•15 citations
The quantum dynamics of an anharmonic oscillator coupled to a bath of up to 60 harmonic oscillators is investigated by a new multiconfigurational hybrid method for wave packet propagation. The method, originally proposed in [Burghardt, Meyer, and Cederbaum, J. Chem. Phys. 111, 2927 (1999)], represents a variant of the multiconfiguration time-dependent Hartree method including a moving basis of Gaussian functions. Energy relaxation and quantum decoherence induced by the zero-temperature oscillator bath are shown to be accurately described by the new method. Decoherence rates for a bath with a discretized ohmic spectral density are found to be consistent with golden-rule predictions for T=0.
A variational approach for the quantum dynamics of statistical mixtures is developed, which is based upon the representation of the natural states of the mixture in terms of hybrid Gaussian-based Multiconfiguration Time-Dependent Hartree (G-MCTDH) wavefunctions. The method, termed ρG-MCTDH, is combined with a treatment of dissipation and decoherence based on the nonstochastic open-system Schrödinger equations. The performance and the convergence properties of the approach are illustrated for a two-dimensional tunneling system, where the primary tunneling coordinate, represented by flexible single-particle functions, is resonantly coupled to a second harmonic mode, represented by Gaussian wave packets. The harmonic coordinate is coupled to the environment and two different processes are studied: (i) vibrational relaxation at zero temperature described by a master equation in the Lindblad form and (ii) thermalization induced by the Caldeira-Leggett master equation. In the second case, the evolution from a quantum tunneling regime to a quasistationary classical-limit distribution, driven by the heat bath, is visualized using a flux analysis.