Semiclassical description of quantum coherence effects and their quenching: A forward–backward initial value representation study

Wang, Haobin; Thoss, Michael; Sorge, Kathy L.; Gelabert, Ricard; Giménez, Xavier; Miller, William H.

doi:10.1063/1.1337802

Cited by 123 publications

(94 citation statements)

References 72 publications

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“…As a final note, in this subsection we have confirmed that for nuclear DOF, the distribution of coordinates 45 or momenta 10 produced by methods that employ mean-field Ehrenfest-like forces such as LSC-IVR can be qualitatively in error. As we will demonstrate in Subsection III B this can have profound problems for predicting electronic state relaxation dynamics with such approaches, though these problems are mitigated to a significant extend for some mean-field like methods such as the PLDM propagation approach.…”

Section: A Nuclear Phase Space Distributions From Linearized and Itmentioning

confidence: 53%

“…These well-known disadvantages of mean-field like methods can be addressed by surface hopping schemes 1, 46 but many such approaches involve ad hoc steps in their implementation. The forward-backward IVR (FB-IVR) approach 10,45,47 provides a relatively inexpensive alternative that is derivable from first principles and can solve these problems in many situations. The iterative linearized short time approximate propagation methods outlined here are also based on well-defined approximations and overcome the problems associated with meanfield propagation and can be made very competitive in computational cost.…”

Section: A Nuclear Phase Space Distributions From Linearized and Itmentioning

confidence: 99%

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Consistent schemes for non-adiabatic dynamics derived from partial linearized density matrix propagation

Huo¹,

Coker²

2012

The Journal of Chemical Physics

102

115

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Powerful approximate methods for propagating the density matrix of complex systems that are conveniently described in terms of electronic subsystem states and nuclear degrees of freedom have recently been developed that involve linearizing the density matrix propagator in the difference between the forward and backward paths of the nuclear degrees of freedom while keeping the interference effects between the different forward and backward paths of the electronic subsystem described in terms of the mapping Hamiltonian formalism and semi-classical mechanics. Here we demonstrate that different approaches to developing the linearized approximation to the density matrix propagator can yield a mean-field like approximate propagator in which the nuclear variables evolve classically subject to Ehrenfest-like forces that involve an average over quantum subsystem states, and by adopting an alternative approach to linearizing we obtain an algorithm that involves classical like nuclear dynamics influenced by a quantum subsystem state dependent force reminiscent of trajectory surface hopping methods. We show how these different short time approximations can be implemented iteratively to achieve accurate, stable long time propagation and explore their implementation in different representations. The merits of the different approximate quantum dynamics methods that are thus consistently derived from the density matrix propagator starting point and different partial linearization approximations are explored in various model system studies of multi-state scattering problems and dissipative non-adiabatic relaxation in condensed phase environments that demonstrate the capabilities of these different types of approximations for treating non-adiabatic electronic relaxation, bifurcation of nuclear distributions, and the passage from nonequilibrium coherent dynamics at short times to long time thermal equilibration in the presence of a model dissipative environment.

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Section: A Nuclear Phase Space Distributions From Linearized and Itmentioning

confidence: 53%

Section: A Nuclear Phase Space Distributions From Linearized and Itmentioning

confidence: 99%

Consistent schemes for non-adiabatic dynamics derived from partial linearized density matrix propagation

Huo¹,

Coker²

2012

The Journal of Chemical Physics

102

115

View full text Add to dashboard Cite

show abstract

“…The analytic and computational results shed new light on decoherence, dynamics of quantum entanglement, and quantum chaos. This study is also of interest to semiclassical decoherence studies [9], e.g., semiclassical descriptions of intrinsic decoherence dynamics in large molecular systems [2]. This paper is organized as follows.…”

Section: Introductionmentioning

confidence: 99%

Intrinsic decoherence dynamics in smooth Hamiltonian systems: Quantum-classical correspondence

Gong

Brumer

2003

Phys. Rev. A

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A direct classical analog of the quantum dynamics of intrinsic decoherence in Hamiltonian systems, characterized by the time dependence of the linear entropy of the reduced density operator, is introduced. The similarities and differences between the classical and quantum decoherence dynamics of an initial quantum state are exposed using both analytical and computational results. In particular, the classicality of early-time intrinsic decoherence dynamics is explored analytically using a second-order perturbative treatment, and an interesting connection between decoherence rates and the stability nature of classical trajectories is revealed in a simple approximate classical theory of intrinsic decoherence dynamics. The results offer new insights into decoherence, dynamics of quantum entanglement, and quantum chaos.

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“…Although the above "time-dependent" approach has been widely used for the explicit computation of thermal rate constants [40][41][42], it presents many numerical problems. In particular,…”

Section: The Time-dependent Approachmentioning

confidence: 99%

Deep nuclear resonant tunneling thermal rate constant calculations

Mandrà

Valleau

Ceotto

2013

Int J of Quantum Chemistry

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A fast and robust time‐independent method to calculate thermal rate constants in the deep resonant tunneling regime for scattering reactions is presented. The method is based on the calculation of the cumulative reaction probability which, once integrated, gives the thermal rate constant. We tested our method with both continuous (single and double Eckart barriers) and discontinuous first derivative potentials (single and double rectangular barriers). Our results show that the presented method is robust enough to deal with extreme resonating conditions such as multiple barrier potentials. Finally, the calculation of the thermal rate constant for double Eckart potentials with several quasi‐bound states and the comparison with the time‐independent log‐derivative method are reported. An implementation of the method using the Mathematica Suite is included in the Supporting Information. © 2013 Wiley Periodicals, Inc.

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Semiclassical description of quantum coherence effects and their quenching: A forward–backward initial value representation study

Cited by 123 publications

References 72 publications

Consistent schemes for non-adiabatic dynamics derived from partial linearized density matrix propagation

Consistent schemes for non-adiabatic dynamics derived from partial linearized density matrix propagation

Intrinsic decoherence dynamics in smooth Hamiltonian systems: Quantum-classical correspondence

Deep nuclear resonant tunneling thermal rate constant calculations

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