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arXiv:1701.05713 · The Journal of Chemical Physics

A unified stochastic formulation of dissipative quantum dynamics. II. Beyond linear response of spin baths

Chang‐Yu Hsieh, Jianshu Cao

Published Jan 2, 2018• 68 citations
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Abstract

We use the “generalized hierarchical equation of motion” proposed in Paper I [C.-Y. Hsieh and J. Cao, J. Chem. Phys. 148, 014103 (2018)] to study decoherence in a system coupled to a spin bath. The present methodology allows a systematic incorporation of higher-order anharmonic effects of the bath in dynamical calculations. We investigate the leading order corrections to the linear response approximations for spin bath models. Two kinds of spin-based environments are considered: (1) a bath of spins discretized from a continuous spectral density and (2) a bath of localized nuclear or electron spins. The main difference resides with how the bath frequency and the system-bath coupling parameters are distributed in an environment. When discretized from a continuous spectral density, the system-bath coupling typically scales as ∼1/NB where NB is the number of bath spins. This scaling suppresses the non-Gaussian characteristics of the spin bath and justifies the linear response approximations in the thermodynamic limit. For the nuclear/electron spin bath models, system-bath couplings are directly deduced from spin-spin interactions and do not necessarily obey the 1/NB scaling. It is not always possible to justify the linear response approximations in this case. Furthermore, if the spin-spin Hamiltonian is highly symmetrical, there exist additional constraints that generate highly non-Markovian and persistent dynamics that is beyond the linear response treatments.

DOI
10.1063/1.5018726

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We use the “generalized hierarchical equation of motion” proposed in Paper I [C.-Y. Hsieh and J. Cao, J. Chem. Phys. 148, 014103 (2018)] to study decoherence in a system coupled to a spin bath. The present methodology allows a systematic incorporation of higher-order anharmonic effects of the bath in dynamical calculations. We investigate the leading order corrections to the linear response approximations for spin bath models. Two kinds of spin-based environments are considered: (1) a bath of spins discretized from a continuous spectral density and (2) a bath of localized nuclear or electron spins. The main difference resides with how the bath frequency and the system-bath coupling parameters are distributed in an environment. When discretized from a continuous spectral density, the system-bath coupling typically scales as ∼1/NB where NB is the number of bath spins. This scaling suppresses the non-Gaussian characteristics of the spin bath and justifies the linear response approximations in the thermodynamic limit. For the nuclear/electron spin bath models, system-bath couplings are directly deduced from spin-spin interactions and do not necessarily obey the 1/NB scaling. It is not always possible to justify the linear response approximations in this case. Furthermore, if the spin-spin Hamiltonian is highly symmetrical, there exist additional constraints that generate highly non-Markovian and persistent dynamics that is beyond the linear response treatments.
We use the "generalized hierarchical equation of motion" proposed in Paper I [C.-Y. Hsieh and J. Cao, J. Chem. Phys. 148, 014103 (2018)] to study decoherence in a system coupled to a spin bath. The present methodology allows a systematic incorporation of higher-order anharmonic effects of the bath in dynamical calculations. We investigate the leading order corrections to the linear response approximations for spin bath models. Two kinds of spin-based environments are considered: (1) a bath of spins discretized from a continuous spectral density and (2) a bath of localized nuclear or electron spins. The main difference resides with how the bath frequency and the system-bath coupling parameters are distributed in an environment. When discretized from a continuous spectral density, the system-bath coupling typically scales as ∼1/NB where N B is the number of bath spins. This scaling suppresses the non-Gaussian characteristics of the spin bath and justifies the linear response approximations in the thermodynamic limit. For the nuclear/electron spin bath models, system-bath couplings are directly deduced from spin-spin interactions and do not necessarily obey the 1/NB scaling. It is not always possible to justify the linear response approximations in this case. Furthermore, if the spin-spin Hamiltonian is highly symmetrical, there exist additional constraints that generate highly non-Markovian and persistent dynamics that is beyond the linear response treatments.
We extend a standard stochastic theory to study open quantum systems coupled to a generic quantum environment. We exemplify the general framework by studying a two-level quantum system coupled bilinearly to the three fundamental classes of non-interacting particles: bosons, fermions, and spins. In this unified stochastic approach, the generalized stochastic Liouville equation (SLE) formally captures the exact quantum dissipations when noise variables with appropriate statistics for different bath models are applied. Anharmonic effects of a non-Gaussian bath are precisely encoded in the bath multi-time correlation functions that noise variables have to satisfy. Starting from the SLE, we devise a family of generalized hierarchical equations by averaging out the noise variables and expand bath multi-time correlation functions in a complete basis of orthonormal functions. The general hierarchical equations constitute systems of linear equations that provide numerically exact simulations of quantum dynamics. For bosonic bath models, our general hierarchical equation of motion reduces exactly to an extended version of hierarchical equation of motion which allows efficient simulation for arbitrary spectral densities and temperature regimes. Similar efficiency and flexibility can be achieved for the fermionic bath models within our formalism. The spin bath models can be simulated with two complementary approaches in the present formalism. (I) They can be viewed as an example of non-Gaussian bath models and be directly handled with the general hierarchical equation approach given their multi-time correlation functions. (II) Alternatively, each bath spin can be first mapped onto a pair of fermions and be treated as fermionic environments within the present formalism.
We investigate the quantum dynamics of a spin coupling to a bath of independent spins via the dissipaton equation of motion (DEOM) approach. The bath, characterized by a continuous spectral density function, is composed of spins that are independent level systems described by the su(2) Lie algebra, representing an environment with a large magnitude of anharmonicity. Based on the previous work by Suarez and Silbey [J. Chem. Phys. 95, 9115 (1991)] and by Makri [J. Chem. Phys. 111, 6164 (1999)] that the spin bath can be mapped to a Gaussian environment under its linear response limit, we use the time-domain Prony fitting decomposition scheme to the bare-bath time correlation function (TCF) given by the bosonic fluctuation-dissipation theorem to generate the exponential decay basis (or pseudo modes) for DEOM construction. The accuracy and efficiency of this strategy have been explored by a variety of numerical results. We envision that this work provides new insights into extending the hierarchical equations of motion and DEOM approach to certain types of anharmonic environments with arbitrary TCF or spectral density.
An approach to non-Markovian system-environment dynamics is described which is based on the construction of a hierarchy of coupled effective environmental modes that is terminated by coupling the final member of the hierarchy to a Markovian bath. For an arbitrary environment, which is linearly coupled to the subsystem, the discretized spectral density is replaced by a series of approximate spectral densities involving an increasing number of effective modes. This series of approximants, which are constructed analytically in this paper, guarantees the accurate representation of the overall system-plus-bath dynamics up to increasing times. The hierarchical structure is manifested in the approximate spectral densities in the form of the imaginary part of a continued fraction similar to Mori theory. The results are described for cases where the hierarchy is truncated at the first-, second-, and third-order level. It is demonstrated that the results generated from a reduced density matrix equation of motion and large dimensional system-plus-bath wavepacket calculations are in excellent agreement. For the reduced density matrix calculations, the system and hierarchy of effective modes are treated explicitly and the effects of the bath on the final member of the hierarchy are described by the Caldeira-Leggett equation and its generalization to zero temperature.
The dynamics of a two-level system coupled to a spin bath is investigated via the numerically exact multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) theory. Consistent with the previous work on linear response approximation [N. Makri, J. Phys. Chem. B 103, 2823 (1999)], it is demonstrated numerically that this spin-spin-bath model can be mapped onto the well-known spin-boson model if the system-bath coupling strength obeys an appropriate scaling behavior. This linear response mapping, however, may require many bath spin degrees of freedom to represent the practical continuum limit. To clarify the discrepancies resulted from different approximate treatments of this model, the population dynamics of the central two-level system has been investigated near the transition boundary between the coherent and incoherent motions via the ML-MCTDH method. It is found that increasing temperature favors quantum coherence in the nonadiabatic limit of this model, which corroborates the prediction in the previous work [J. Shao and P. Hanggi, Phys. Rev. Lett. 81, 5710 (1998)] based on the non-interacting blip approximation (NIBA). However, the coherent-incoherent boundary obtained by the exact ML-MCTDH simulation is slightly different from the approximate NIBA results. Quantum dynamics in other physical regimes are also discussed.
Over decades, the theoretical study of the quantum dissipative dynamics was mainly based on the linear dissipation model. The study of the nonlinear dissipative dynamics in condensed phases, where there exist an infinite number of bath modes, is extremely difficult even if not impossible. This work put forward a stochastic scheme for the simulation of the nonlinear dissipative dynamics. In the linear response regime, the second-order cumulant expansion becomes exact to reproduce the effect of the bath on the evolution of the reduced system. Consequently, a Hermitian stochastic Liouville equation is derived without explicit treatment of the bath. Stochastic simulations for an anharmonic model illustrate that the dynamics dissipated by anharmonic bath exhibits substantial difference on temperature dependence compared to that with the Caldeira-Leggett model.