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 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.
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.
Wave function methods have offered a robust, systematically improvable means to study the 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. Analogs 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. Approximating every state in the Hilbert space is an impossible task. Besides, excited-state theories are not as well studied as ground-state ones. In this thesis, we overcome these difficulties by employing thermofield dynamics, a theory that allows the purification of the ensemble density matrix and constructs a pure wave function that encodes the equilibrium thermal behavior of the system. Ensemble averages become expectation values over this so-called thermal state. Around this thermal state, we develop a framework to extend ground-state wave function theories to non-zero temperatures. We discuss explicit formulations of mean-field, configuration interaction, and coupled cluster theories for thermal properties of fermions in the grand canonical ensemble. For fermions in the canonical ensemble, we present mean-field, configuration interaction, and perturbation theories. We also discuss thermal mean-field, configuration interaction, and coupled cluster formalisms for \SU systems. To assess the quality of these approximations, we study both model and small atomic and molecular as benchmark electronic problems while comparing against exact results. For spins, we use the Lipkin-Meshkov-Glick and the one-dimensional transverse field Ising models as our reference systems. Indeed, the thermal methods perform reasonably well while merely adding a prefactor to the computational cost. They also inherit all the properties, good or bad, from their ground-state counterparts, signifying the robustness of our formalism.
Thermofield dynamics has proven to be a very useful theory in high-energy physics, particularly since it permits the treatment of both time- and temperature-dependence on an equal footing. We here show that it also has an excellent potential for studying thermal properties of electronic systems in physics and chemistry. We describe a general framework for constructing finite temperature correlated wave function methods typical of ground state methods. We then introduce two distinct approaches to the resulting imaginary time Schrödinger equation, which we refer to as fixed-reference and covariant methods. As an example, we derive the two corresponding versions of thermal configuration interaction theory and apply them to the Hubbard model, while comparing with exact benchmark results.
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.
A vibrational electronic-thermofield coupled cluster (VE-TFCC) approach is developed to calculate thermal properties of non-adiabatic vibronic coupling systems. The thermofield (TF) theory and a mixed linear exponential ansatz based on second-quantized Bosonic construction operators are introduced to propagate the thermal density operator as a “pure state” in the Bogoliubov representation. Through this compact representation of the thermal density operator, the approach is basis-set-free and scales classically (polynomial) as the number of degrees of freedoms (DoF) in the system increases. The VE-TFCC approach is benchmarked with small test models and a real molecular compound (CoF 4 – anion) against the conventional sum over states (SOS) method and applied to calculate thermochemistry properties of a gas-phase reaction: CoF 3 + F – → CoF 4 – . Results shows that the VE-TFCC approach, in conjunction with vibronic models, provides an effective protocol for calculating thermodynamic properties of vibronic coupling systems.
At zero temperature, coupled cluster theories are widely used to predict total energies, ground state expectation values, and even excited states for molecules and extended systems. However, for systems with a small band gap, such as metals, the zero-temperature approximation does not necessarily hold. Thermal effects may even give rise to interesting chemistry on metal surfaces. Most approaches to temperature dependent electronic properties employ finite temperature perturbation theory in the Matsubara frequency formulation. Computations require a large number of Matsubara frequencies to yield sufficiently accurate results, especially at low temperatures. This work, and independently the work of White and Chan J. Chem. Theory Comput. 2018 , DOI: 10.1021/acs.jctc.8b00773 , proposes a coupled cluster implementation directly in the imaginary time domain on the compact interval [0, β], closely related to the thermal cluster cumulant approach of Sanyal et al. [ Chem. Phys. Lett. 1992 , 192 , 55 - 61 ] , Sanyal et al. [ Phys. Rev. E 1993 , 48 , 3373 - 3389 ], and Mandal et al. [ Int. J. Mod. Phys. B 2003 , 17 , 5367 - 5377 ]. Here, the arising imaginary time dependent coupled cluster amplitude integral equations are solved in the linearized direct ring doubles approximation, also referred to as Tamm-Dancoff approximation with second order (linearized) screened exchange. In this framework, the transition from finite to zero temperature is uniform and comes at no extra costs, allowing to go to temperatures as low as room temperature. In this approximation, correlation grand potentials are calculated over a wide range of temperatures for solid lithium, a metallic system, and for solid silicon, a semiconductor.