We extend the coupled-cluster method to correlated quantum dynamics of both closed and open systems at finite temperatures using the thermofield formalism. The approach expresses the time-dependent density matrix in an exponential ansatz and describes time-evolution along the Keldysh path contour. A distinct advantage of the approach is exact trace-preservation as a function of time, ensuring conservation of probability and particle number. Furthermore, the method avoids the computation of correlated bra-states, simplifying the computational implementation. We develop the method in a thermal quasiparticle representation, which allows seamless connection to the projection method and diagrammatic techniques of the traditional coupled-cluster formalism. For comparison, we also apply the thermofield framework to the density-matrix renormalization-group method to obtain reference results for closed and open systems at finite temperature. We test the singles and doubles approximation to the density-matrix coupled-cluster method on the correlated electronic dynamics of the single-impurity Anderson model, demonstrating that the new method successfully captures the correlated dynamics of both closed systems at finite temperature and driven-dissipative open systems. This encouraging performance motivates future applications to nonequilibrium quantum many-body dynamics in realistic systems.
We extend the coupled-cluster method to correlated quantum dynamics of both closed and open systems at finite temperatures using the thermofield formalism. The approach expresses the time-dependent density matrix in an exponential ansatz and describes time-evolution along the Keldysh path contour. A distinct advantage of the approach is exact trace-preservation as a function of time, ensuring conservation of probability and particle number. Furthermore, the method avoids the computation of correlated bra-states, simplifying the computational implementation. We develop the method in a thermal quasiparticle representation, which allows seamless connection to the projection method and diagrammatic techniques of the traditional coupled-cluster formalism. For comparison, we also apply the thermofield framework to the density-matrix renormalization-group method to obtain reference results for closed and open systems at finite temperature. We test the singles and doubles approximation to the density-matrix coupled-cluster method on the correlated electronic dynamics of the single-impurity Anderson model, demonstrating that the new method successfully captures the correlated dynamics of both closed systems at finite temperature and driven-dissipative open systems. This encouraging performance motivates future applications to nonequilibrium quantum many-body dynamics in realistic systems.
We present a coupled cluster and linear response theory to compute properties of many-electron systems at nonzero temperatures. For this purpose, we make use of the thermofield dynamics, which allows for a compact wave function representation of the thermal density matrix, and extend our recently developed framework ( J. Chem. Phys. 2019, 150, 154109, DOI: 10.1063/1.5089560 ) to parametrize the so-called thermal state using an exponential ansatz with cluster operators that create thermal quasiparticle excitations on a mean-field reference. As benchmark examples, we apply this method to both model (one-dimensional Hubbard and Pairing) and ab initio (atomic Beryllium and molecular Hydrogen) systems, while comparing with exact results.
We extend the finite-temperature Keldysh non-equilibrium coupled cluster theory (Keldysh-CC) [A. F. White and G. K.-L. Chan, J. Chem. Theory Comput. 15, 6137–6253 (2019)] to include a time-dependent orbital basis. When chosen to minimize the action, such a basis restores local and global conservation laws (Ehrenfest’s theorem) for all one-particle properties while remaining energy conserving for time-independent Hamiltonians. We present the time-dependent Keldysh orbital-optimized coupled cluster doubles method in analogy with the formalism for zero-temperature dynamics, extended to finite temperatures through the time-dependent action on the Keldysh contour. To demonstrate the conservation property and understand the numerical performance of the method, we apply it to several problems of non-equilibrium finite-temperature dynamics: a 1D Hubbard model with a time-dependent Peierls phase, laser driving of molecular H2, driven dynamics in warm-dense silicon, and transport in the single impurity Anderson model.
We leverage the Keldysh formalism to extend our implementation of finite temperature coupled cluster theory [ J. Chem. Theory Comput. 2018, 14, 5690–5700] to thermal systems that have been driven out of equilibrium. The resulting Keldysh coupled cluster theory is discussed in detail. We describe the implementation of the equations necessary to perform Keldysh coupled cluster singles and doubles calculations of finite-temperature dynamics, and we apply the method to some simple systems including a Hubbard model with a Peierls phase and an ab initio model of warm-dense silicon subject to an ultrafast XUV pulse.
Wave function methods have offered a robust, systematically improvable means to study ground-state properties in quantum many-body systems. Theories like coupled cluster and their derivatives provide highly accurate approximations to the energy landscape at a reasonable computational cost. Analogues of such methods to study thermal properties, though highly desirable, have been lacking because evaluating thermal properties involve a trace over the entire Hilbert space, which is a formidable task. Besides, excited-state theories are generally not as well studied as ground-state ones. In this mini-review, we present an overview of a finite-temperature wave function formalism based on thermofield dynamics to overcome these difficulties. Thermofield dynamics allows us to map the equilibrium thermal density matrix to a pure state, i.e., a single wave function, albeit in an expanded Hilbert space. Ensemble averages become expectation values over this so-called thermal state. Around this thermal state, we have developed a procedure to generalize ground-state wave function theories to finite temperatures. As explicit examples, we highlight formulations of mean-field, configuration interaction, and coupled cluster theories for thermal properties of Fermions in the grand-canonical ensemble. To assess the quality of these approximations, we also show benchmark studies for the one-dimensional Hubbard model, while comparing against exact results. We will see that the thermal methods perform similarly to their ground-state counterparts, while merely adding a prefactor to the asymptotic computational cost. They also inherit all the properties, good or bad, from the ground-state methods, signifying the robustness of our formalism and the scope for future development.
We apply the recently developed real-time renormalization-group (RTRG) method to different quantum dissipative systems. In contrast to other renormalization-group techniques the RTRG approach is formulated on the Keldysh contour and therefore allows for the description of nonequilibrium situations. The method is based on an exact kinetic equation which determines the time-dependent reduced density matrix. The kinetic equation involves an integral kernel which describes the phenomenon of dissipation. We calculate this quantity using the RTRG method: After applying Wick's theorem the arising diagrams are accounted for successively with respect to their time scale. During that process the theory is left invariant by renormalizing the operators describing the theory. As a starting point we discuss the polaron problem. We calculate the renormalized ground-state energy and the effective mass. We compare our results of the RTRG with those obtained from the flow equation formalism, which is based on infinitesimal transformations. In the central part of this thesis we consider the spin-boson model which is applicable to various physical and chemical systems. It models a particle in a double-well potential which is coupled to a bosonic environment. We determine static properties such as the static susceptibility. We also present results for the time evolution of the reduced density matrix starting from an arbitrary nonequilibrium state. The asymptotic behaviour of the reduced density matrix can be characterized by an oscillation frequency and two decay constants, all of which are determined. Finally, we calculate equilibrium correlation functions. We find consistency of our results with quantum Monte Carlo simulations and with the Shiba-relation. Additionally, our results show the correct scaling behaviour. Comparisons are also drawn to results of the noninteracting blip approximation and to results obtained for the anisotropic Kondo model. Our approach is very accurate for not too large couplings to the environment. Furthermore, the stationary tunnel current through a double quantum dot coupled to a phonon bath is calculated and compared to experimental data. Eventually, the running couplings of the two-lead Kondo model are discussed.
We introduce a method, numerically exact in principle, for computing the momentum- and frequency-resolved single-particle Green's function of a polaron at finite temperature. The method, which we refer to as the finite-temperature Green's function cluster expansion, combines two ingredients: the generalized Green's function cluster expansion, a numerically exact extension of the momentum average family of methods that solves the polaron problem at zero temperature through a hierarchy of equations of motion for restricted phonon cloud configurations; and the thermofield double formalism, which maps the thermal trace onto a pure-state expectation value over a doubled Hilbert space. The resulting equations of motion have the same algebraic structure as those of the multi-boson zero-temperature theory, with the temperature entering through a Bogoliubov-type mixing angle that controls the coupling to a set of fictitious bath bosons. We implement the method in our open-source software package and benchmark it on the one-dimensional Holstein polaron, computing spectral functions, dispersions, lifetimes, and effective masses across coupling regimes and temperatures up to T/Ω∼1. Where finite-temperature density matrix renormalization group results are available, we find quantitative agreement at affordable computational cost. The method recovers momentum-resolved spectra directly in frequency space, with no time evolution or analytic continuation. We also discuss the practical costs of the approach. In particular, since the doubled phonon Hilbert space has a non-trivial configuration structure in which real and fictitious clouds compete, convergence in the corresponding cloud parameters requires care.