Matsubara dynamics has recently emerged as the most general form of a quantum-Boltzmann-conserving classical dynamics theory for the calculation of single-time correlation functions. Here, we present a generalization of Matsubara dynamics for the evaluation of multitime correlation functions. We first show that the Matsubara approximation can also be used to approximate the two-time symmetrized double Kubo transformed correlation function. By a straightforward extension of these ideas to the multitime realm, a multitime Matsubara dynamics approximation can be obtained for the multitime fully symmetrized Kubo transformed correlation function. Although not a practical method, due to the presence of a phase-term, this multitime formulation of Matsubara dynamics represents a benchmark theory for future development of Boltzmann preserving semiclassical approximations to general higher order multitime correlation functions. It also reveals a connection between imaginary time-ordering in the path integral and the classical dynamics of multitime correlation functions.
Matsubara dynamics has recently emerged as the most general form of a quantum-Boltzmann-conserving classical dynamics theory for the calculation of single-time correlation functions. Here, we present a generalization of Matsubara dynamics for the evaluation of multitime correlation functions. We first show that the Matsubara approximation can also be used to approximate the two-time symmetrized double Kubo transformed correlation function. By a straightforward extension of these ideas to the multitime realm, a multitime Matsubara dynamics approximation can be obtained for the multitime fully symmetrized Kubo transformed correlation function. Although not a practical method, due to the presence of a phase-term, this multitime formulation of Matsubara dynamics represents a benchmark theory for future development of Boltzmann preserving semiclassical approximations to general higher order multitime correlation functions. It also reveals a connection between imaginary time-ordering in the path integral and the classical dynamics of multitime correlation functions.
The general properties of time dependent autocorrelations in many-body quantum systems are here analyzed at thermodynamic equilibrium in the Boltzmann canonical ensemble at temperature T, by means of the exponential expansion theory (EET). It is shown that the Kubo-Martin-Schwinger (KMS) symmetry applied to the exponential expansion of the correlation leads to the existence of two different sets of decay modes (channels) here indicated as "Matsubara modes" and "system modes," respectively. The Matsubara modes are a series of pure decay channels with time constants representing a direct action of the thermostat upon the correlation, with a characteristic principal decay time τ_{1}=ℏ/(2πk_{B}T), where ℏ and k_{B} are the Planck and Boltzmann constants, and T is the temperature. Moreover, the KMS condition implies that the amplitudes pertaining to the even and odd contribution of the system modes to the quantum correlation are not independent. These two properties are quantum mechanical in nature and "universal," in the sense that they are present for any autocorrelation of a quantum system at equilibrium at a temperature T. The Matsubara modes' contribution to the time behavior of a quantum correlation is limited to times of the order of τ_{1}, which however can be comparable with some of the characteristic decay times of the system modes. In addition, since the parameters representing the overall time behavior of the quantum correlation can be given in terms of the parameters of its Kubo transform, the EET representation turns out to be useful in calculations exploiting the outputs of some widespread quantum simulation methods. A discussion of the properties of these relations is described in detail with numerical examples. The case of the velocity autocorrelation function of para hydrogen at low temperature is also reported as a final example for a real system.
We develop an exact quantum thermostat that generates the quantum Boltzmann distribution in path integral phase space and so correctly captures the imaginary position–momentum correlations. This extends beyond the capability of existing quantum thermostats such as the PILE thermostat, which can only achieve the marginal of this distribution in position, with the momentum acting purely as a sampling tool and satisfying classical Maxwell–Boltzmann statistics. The dynamics correspond to the treatment of the Caldeira–Leggett system–bath model with Matsubara dynamics, a theory for approximating nuclear quantum dynamics by propagating smooth imaginary-time Feynman paths in real time. A Matsubara generalised Langevin equation that obeys certain quantum fluctuation–dissipation relations is mapped onto a Markovian stochastic process by introducing auxiliary variables; this allows the construction of a corresponding Fokker–Planck equation from which the stationary distribution in the extended variable space is determined. We show that this corresponds to the joint quantum Boltzmann distribution in position and momentum, a finding that holds for any bath spectral density and for anharmonic systems. The sole approximation in Matsubara dynamics is the neglect of real-time quantum coherence; consequently, provided there is sufficient quantum decoherence, the dynamics of the exact quantum thermostat also well approximates the exact quantum dynamics of the system–bath. In the limit of infinite system–bath coupling, the level of real-time coherence becomes negligible and so the Matsubara dynamics of the thermostat tends to the exact dynamics. The quantum thermostat can therefore be used to study this limit exactly and, in so doing, we demonstrate the existence of a quantum mechanical overdamped regime analogous to its classical counterpart that is characterised by a Matsubara Smoluchowski equation. The drawback of the quantum thermostat is that one of its associated quantum fluctuation–dissipation relations is imaginary. This results in complex noise and dynamical instabilities that often preclude the numerical implementation of the thermostat. Instead, it primarily serves as a theoretical framework that can be used as a starting point for introducing approximations that yield more practical methods. One such approximation that results in real noise is considered here and leads to a practical approach for calculating linear time-correlation functions of bound open quantum systems. These exhibit good agreement with exact quantum mechanical calculations, particularly at strong system–bath coupling, where the real-time quantum coherence is increasingly suppressed.
We report the first numerical calculations in which converged Matsubara dynamics is compared directly with exact quantum dynamics with no artificial damping of the time-correlation functions (TCFs). The system treated is a Morse oscillator coupled to a harmonic bath. We show that, when the system-bath coupling is sufficiently strong, the Matsubara calculations can be converged by explicitly including up to M = 200 Matsubara modes, with the remaining modes included as a harmonic "tail" correction. The resulting Matsubara TCFs are in near-perfect agreement with the exact quantum TCFs, for non-linear as well as linear operators, at a temperature at which the TCFs are dominated by quantum thermal fluctuations. These results provide compelling evidence that incoherent classical dynamics can arise in the condensed phase at temperatures at which the statistics are dominated by quantum (Boltzmann) effects, as a result of smoothing of imaginary-time Feynman paths. The techniques developed here may also lead to efficient methods for benchmarking system-bath dynamics in the overdamped regime.
This paper is devoted to the development of an operator formulation of the recent extension of the centroid molecular dynamics method [J. Chem. Phys. 110, 3647 (1999); 111, 5303 (1999)] to boson and fermion systems. An operator calculus is used to rederive the basic equations of centroid dynamics. The following generalization to the case of systems of many indistinguishable particles is based on the use of a projection operator. Two different definitions of the quasi-density operator for bosonic and fermionic systems are suggested. The first definition allows an exact evaluation of equilibrium properties for systems with exchange effects using classical-like molecular dynamics calculations. The second one provides a formal justification of Bose–Einstein/Fermi–Dirac centroid dynamics with the same set of approximations as for Boltzmann statistics, and can be used to extract quantum dynamical information. In this case, the corresponding centroid correlation function can be related to a double Kubo transformed quantum mechanical one.
We present an iterative path integral algorithm for computing multitime correlation functions of a quantum system coupled to a dissipative bath of harmonic oscillators. By splitting the Boltzmann operator into two parts and reordering the propagators in the expression for canonical correlation functions, we are able to transform the evolution time contour into a symmetric one so that a forward propagation and a backward one are specified. Because the memory induced by the bath through the Feynman–Vernon influence functional decays rapidly in the complex time plane, long-time correlations are negligible. Taking advantage of this fact, we show that the correlation function can be obtained via an iterative procedure. The method is used to calculate three-time correlation functions of a dissipative two-level system.
Measuring vibronic spectra probes dynamical processes in molecular systems. When interpreted via suitable theoretical tools, the experimental data provides comprehensive information about the system in question. For complex many-body problems, such an approach usually requires the formulation of proper classical-like approximations, which is particularly challenging if multiple electronic states are involved. In this work, we express the imaginary-time shifted time correlation function and, thus, the vibronic spectrum in terms of the so-called Matsubara dynamics, which combines quantum statistics and classical-like dynamics. By applying the Matsubara approximation in the adiabatic limit, we derive a formal generalization of the existing Matsubara dynamics formalism to multiple potential energy surfaces (PESs), which, however, does not feature all the defining properties of its single-PES counterpart though suffering equally from the sign problem. The mathematical analysis for two shifted harmonic oscillators suggests a new modified method to practically simulate the standard correlation function via Matsubara-like dynamics. Importantly, this modified method samples the thermal Wigner function without suffering from the sign problem and yields an accurate approximation to the vibronic absorption spectrum, not only for the harmonic system but also for the anharmonic one.