Several techniques to solve a hierarchical set of equations of motion for propagating a reduced density matrix coupled to a thermal bath have been developed in recent years. This is either done using the path integral technique as in the original proposal by Tanimura and Kubo [J. Phys. Soc. Jpn. 58, 101 (1998)] or by the use of stochastic fields as done by Yan et al. [Chem. Phys. Lett. 395, 216 (2004)]. Based on the latter ansatz a compact derivation of the hierarchy using a decomposition of the spectral density function is given in the present contribution. The method is applied to calculate the time evolution of the reduced density matrix describing the motion in a harmonic, an anharmonic, and two coupled oscillators where each system is coupled to a thermal bath. Calculations to several orders in the system-bath coupling with two different truncations of the hierarchy are performed. The respective density matrices are used to calculate the time evolution of various system properties and the results are compared and discussed with a special focus on the convergence with respect to the truncation scheme applied.
In a previous paper we showed how time-dependent projection operators may be employed to enable the Nakajima-Zwanzig projection-operator technique for deriving exact master equations to deal efficiently with two or more coupled classical or quantum systems, neither of which is reservoir like. We considered in detail the case where the relevant part of the classical-system probability-density function (PDF) or quantumsystem density operator (DO) is a product of the PDF's or DO's for the separate subsystems, and we applied the techniques developed to problems in quantum optics and in the kinetic theory of dilute nonideal gases. In this paper we make the time-dependent projection-operator approach useful for a greater variety of systems by allowing the relevant part of the PDF or DO to include correlations between two of the interacting subsystems. This extension allows us to describe well the dynamics of strongly interacting systems in a low degree of approximation while avoiding the use of infinite resummations. We derive exact generalized master equations in this manner for the same two cases as in our earlier work, namely a classical gas of
N molecules interacting via a two-body potential and a quantum-optical system of
N two-level atoms interacting with an electromagnetic field. In the former case, the relevant part of the PDF contains two-body correlations, and we obtain two exact coupled master equations for the singlet and doublet PDF's
F1(t) and
F2(t). In the latter case, the relevant part of the DO contains atom-field correlations, and the result is three exact coupled equations for the single-atom DO ${\ensuremath{\rho}}_{1}(t)$, the field DO
R(t), and the DO for one atom plus the field $\ensuremath{\chi}(t)$. From the exact equations we derive approximate equations by making simplifying assumptions. In the case of the gas we carry out a straightforward density expansion of the ${\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{F}}_{2}$ master equation and obtain a set of kinetic equations for dense gases, which have been derived previously by Frieman, Goldman, and Dorfman and which describe well effects due to the finite mean free path. In the quantum-optical case we derive kinetic equations for a single-mode laser by treating the $\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{\ensuremath{\chi}}$ equation in the Born-Markoff approximation. The equations describe gain saturation and other effects on the field dynamics which are of infinite order in the atom-field coupling constant. It is shown that these equations reduce to previously derived laser master equations if atom-atom correlations can be neglected. Finally, we mention possible generalizations of the time-dependent projection-operator approach used in this paper and briefly discuss its application to other problems, including the kinetics of liquids, collisional line broadening, superradiance, and amplified spontaneous emission.
The equations of motion for reduced density matrices form a coupled chain known as the Bogoliubov-Born-Green-Kirkwood-Yvon (BBGKY) hierarchy. To close the coupled chain at the two-body level, approximations for a three-body density matrix with one-body and two-body density matrices are needed. The time-dependent density-matrix theory (TDDM) assumes that the three-body density matrix is given by the antisymmetrized products of the one-body and two-body density matrices. In this review the truncation schemes of the BBGKY hierarchy beyond TDDM are discussed and a formulation for the study of excited states which is derived from the time-dependent approach is explained. The truncation schemes and the formulation for excited states are applied to the Lipkin model and the Hubbard model to corroborate their validity. Two realistic applications of the TDDM approaches are also presented. One is the dipole and quadrupole excitations of
40Ca and
48Ca and the other the fusion reactions of
16O +
16O.
In this paper we derive master equations for two or more systems coupled to each other, perhaps strongly, by using a generalization of the usual projection-operator technique to include time-dependent projection operators. The coupled systems may be either similar or dissimilar and classical or quantum mechanical. Whereas the customary approaches to coupled systems are best able to treat situations in which some of the systems are "baths" with a specified density operator or phase-space probability density, our approach allows us to treat situations where it is necessary or convenient to treat the coupled systems on an equal footing. In our scheme the "relevant" part of the full density operator is considered to be the uncorrelated part of the full density operator and is a symmetric functional of the reduced density operators of each of the coupled subsystems. The "irrelevant" part of the density operator is then the part describing correlations between the coupled systems. Our formalism is particularly useful where systems are coupled to one another predominantly in a self-consistent fashion. First, we develop exact master equations for two coupled systems, taking as our prototype the dynamical problem of quantum optics, where a spatially extended collection of two-level atoms interact with a multimode optical field. We then generalize our results to
N coupled systems, taking as our prototype the kinetics of a classical nonideal gas interacting through two-body forces, and derive exact master equations for the system. We then consider as examples several approximate theories resulting from our exact equations. In the case of the imperfect gas we investigate the low-density limit and show how Bogoliubov's form of the Boltzmann equation emerges from our formalism, as well as corrections due to Klimontovich. We consider as special cases of our exact quantum-optical equations the equations in the first Born approximation, with and without memory, and show how several existing quantum-optical master equations are contained in our general results. As a second example in quantum optics, we consider the case where the predominant behavior of the system is described by the self-consistent-field or coupled Bloch and Maxwell equations and derive a first-order perturbation description for deviations from self-consistent-field behavior.
Time-dependent density functional theory (TDDFT) provides a successful approach to calculate excitation energies of atomic and molecular systems. In part I of this work we present a double-pole approximation (DPA) to the response equations of TDDFT. The double-pole approximation provides an exact description of systems with two strongly coupled excitations which are isolated from the rest of the spectrum. In contrast to the traditional single- pole approximation of TDDFT the DPA also yields corrections to the Kohn-Sham oscillator strengths. Several critical pole separations can be identified, e.g. we find that the pole coupling can cause transitions to vanish entirely from the optical spectrum. We also demonstrate how to invert the double-pole solution which allows us to predict matrix elements of the exchange- correlation kernel fxc from experimental input. This can serve as benchmark for the construction of future approximations for the kernel fxc. Reduced density matrix functional theory (RDMFT) has emerged recently as promising candidate to treat strongly correlated electronic many-body systems beyond traditional density functional theory (DFT). The research within RDMFT was so far focussed on the static theory. In this work we attempt some first steps towards a time-dependent generalization of RDMFT. In part II we derive equations of motion for natural orbitals and occupation numbers. Using the equation of motion for the occupation numbers we show that an adiabatic extension of presently known ground-state functionals of static RDMFT always leads to occupation numbers which are constant in time. From the stationary conditions of the equations of motion for the N-body correlations (correlated parts of the N-body matrices) we derive a new class of ground-state functionals which can be used in static RDMFT. Applications are presented for a one-dimensional model system where the time-dependent many-body Schrödinger equation can be propagated numerically. We use optimal control theory to find optimized laser pulses for transitions in a model for atomic Helium. From the numerically exact correlated wavefunction we extract the exact time evolution of natural orbitals and occupation numbers for (i) laser-driven Helium and (ii) electron-ion scattering. Part III of this work considers time-dependent quantum transport within TDDFT. We present an algorithm for the calculation of extended eigenstates of single- particle Hamiltonians which is especially tailored to a finite-difference discretization of the Schrödinger equation. We consider the propagation of finite mesoscopic systems and demonstrate the limitations of such an approach. To overcome the shortcomings of a description of quantum transport in terms of finite systems we develop a time-propagation scheme for extended states which utilizes a mixed basis representation. Our discretization scheme allows to treat central device and lead regions on the same footing thus preventing artificial reflections at grid boundaries.