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.
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.
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 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 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.
Description of electron correlation is crucial to chemical accuracy in quantum chemical calculations. However, the interaction of electrons in a system is an insoluble many-body problem. Constructing approximations to describe electron correlation is a challenging task, but there has been success in the quantum chemistry community using wavefunction methods and density functional theory. However, there are still challenges to be overcome in areas such as theoretical solid state chemistry, which requires description of large systems and the use of finite temperature. Large system sizes and finite temperature can be difficult to treat solely with the currently available methods. Therefore, a new class of methods, based on the temperature-dependent Green's function, is implemented and explored. This thesis is toward investigating the use of temperature-dependent Green's functions for ab-initio quantum chemistry. That is, we are treating a quantum chemical Hamiltonian with realistic electron interactions. While this formalism has been applied to model systems in the condensed matter community, its has been used much less by the quantum chemistry community. Therefore, the numerical behavior and accuracy of Green's function methods for quantum chemical calculations is relatively unknown. This work investigates the ability of the temperature-dependent Green's function, which is an ensemble formalism, to give access to temperature dependent thermodynamic quantities such as free energy and entropy when calculated in a second-order and perturbative manner (GF2). We find that this method is able to give good accuracy for lower temperatures and excellent accuracy for higher temperatures for a molecular case and is able to qualitatively describe a simple model of a solid. The results of this work are presented in chapter 3. Although Green's functions have a clear connection with spectra at zero temperature, it is not straight forward to obtain spectra from the finite temperature Green's function, which is calculated on the imaginary frequency axis. Therefore, we must investigate methods to obtain spectral quantities in a consistent and reliable manner from the imaginary axis. Chapter 4 investigates several methods to do so and we compare our results with experimental and highly accurate benchmark data. We find that it is possible to obtain spectral quantities that can differ by several electron volts, even if the same level of theory is used to obtain the Green's function. This reiterates that finding a spectrum from the imaginary axis is nontrivial and that one must exercise caution when comparing spectral quantities that were calculated using different techniques, even if they are treated with the same theoretical accuracy. Accessing larger systems with the Green's function requires the use of quantum embedding. Quantum embedding describes nontrivial electron interaction between a highly accurate ``active space'' or ``impurity'' and a larger, lower level ``environment''. It is challenging to construct an impurity solver that is reliable at low temperatures. In chapter 5 of this work, we implement and test a temperature dependent configuration interaction impurity solver for quantum embedding. This solver can be used in quantum embedding schemes such as dynamical mean field theory and self-energy embedding theory for larger systems. Overall, this thesis has made progress toward using Green's functions for ab-initio quantum chemistry at finite temperature. Groundwork has been laid for using this formalism to calculate thermodynamics and spectra using a Green's function with realistic electron interactions and to explore quantum embedding using an impurity solver at low temperatures.
The Gaussian wavefunctional approach is developed in thermofield dynamics. We construct the thermal vacuum wavefunctional, its creation as well as annihilation operators, and accordingly the thermo-particle excited states. For a ( D + 1)-dimensional scalar field system with an arbitrary potential whose Fourier representation exists in the sense of tempered distributions, we calculate the finite-temperature Gaussian effective potential (FTGEP), one- and two-thermo-particle-state energies. The zero-temperature limit of each of them is just the corresponding result in quantum field theory, and the FTGEP can lead to the same one for some concrete models as calculated by the imaginary-time Green function.
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.