We introduce renormalized integrals which generalize conventional measure theoretic integrals. One approximates the integration domain by measure spaces and defines the integral as the limit of integrals over the approximating spaces. This concept is implicitly present in many mathematical contexts such as Cauchy's principal value, the determinant of operators on a Hilbert space and the Fourier transform of an L^p function. We use renormalized integrals to define a path integral on manifolds by approximation via geodesic polygons. The main part of the paper is dedicated to the proof of a path integral formula for the heat kernel of any self-adjoint generalized Laplace operator acting on sections of a vector bundle over a compact Riemannian manifold.

The quantum simulation of large molecular systems is a formidable task. We explore the use of effective potentials based on the Feynman path centroid variable in order to simulate large quantum clusters at a reduced computational cost. This centroid can be viewed as the “most” classical variable of a quantum system. Earlier work has shown that one can use a pairwise centroid pseudo-potential to simulate the quantum dynamics of hydrogen in the bulk phase at 25 K and 14 K [Chem. Phys. Lett. 249, 231, (1996)]. Bulk hydrogen, however, freezes below 14 K, so we focus on hydrogen clusters and nanodroplets in the very low temperature regime in order to study their structural behaviours. The calculation of the effective centroid potential is addressed along with its use in the context of molecular dynamics simulations. The effective pseudo-potential of a cluster is temperature dependent and shares similar behaviour as that in the bulk phase. Centroid structural properties in three dimensional space are presented and compared to the results of reference path-integral Monte Carlo simulations. The centroid pseudo-potential approach yields a great reduction in computation cost. With large cluster sizes, the approximate pseudo-potential results are in agreement with the exact reference calculations. An approach to deconvolute centroid structural properties in order to obtain real space results for hydrogen clusters of a wide range of sizes is also presented. The extension of the approach to the treatment of confined hydrogen is discussed, and concluding remarks are presented.

Understanding energy transfer at the molecular scale is both essential for the design of novel molecular level devices and vital for uncovering the fundamental properties of non-equilibrium open quantum systems. In this thesis, we first establish the connection between molecular scale devices -- molecular electronics and phononics -- and open quantum system models. We then develop theoretical tools to study various properties of these models. We extend the standard master equation method to calculate the steady state thermal current and conductance coefficients. We then study the scaling laws of the thermal current with molecular chain size and energy, and apply this tool to investigate the onset of nonlinear thermal current - temperature characteristics, thermal rectification and negative differential conductance. Our master equation technique is valid in the ``on-resonance" regime, referring to the situation in which bath modes in resonance with the subsystem modes are thermally populated. In the opposite ``off-resonance" limit, we develop the Energy Transfer Born-Oppenheimer method to obtain the thermal current scaling without the need to solve for the subsystem dynamics. Finally, we develop a mapping scheme that allows the dynamics of a class of open quantum systems containing coupled subsystems to be treated by considering the separate dynamics in different subsections of the Hilbert space. We combine this mapping scheme with path integral numerical simulations to explore the rich phenomenon of entanglement dynamics within a dissipative two-qubit model. The formalisms developed in this thesis could be applied for the study of energy transfer in different realizations, including molecular electronic junctions, donor-acceptor molecules, artificial solid state qubits and cold-atom lattices.

Understanding energy transfer at the molecular scale is both essential for the design of novel molecular level devices and vital for uncovering the fundamental properties of non-equilibrium open quantum systems. In this thesis, we first establish the connection between molecular scale devices -- molecular electronics and phononics -- and open quantum system models. We then develop theoretical tools to study various properties of these models. We extend the standard master equation method to calculate the steady state thermal current and conductance coefficients. We then study the scaling laws of the thermal current with molecular chain size and energy, and apply this tool to investigate the onset of nonlinear thermal current - temperature characteristics, thermal rectification and negative differential conductance. Our master equation technique is valid in the ``on-resonance" regime, referring to the situation in which bath modes in resonance with the subsystem modes are thermally populated. In the opposite ``off-resonance" limit, we develop the Energy Transfer Born-Oppenheimer method to obtain the thermal current scaling without the need to solve for the subsystem dynamics. Finally, we develop a mapping scheme that allows the dynamics of a class of open quantum systems containing coupled subsystems to be treated by considering the separate dynamics in different subsections of the Hilbert space. We combine this mapping scheme with path integral numerical simulations to explore the rich phenomenon of entanglement dynamics within a dissipative two-qubit model. The formalisms developed in this thesis could be applied for the study of energy transfer in different realizations, including molecular electronic junctions, donor-acceptor molecules, artificial solid state qubits and cold-atom lattices.

The quantum simulation of large molecular systems is a formidable task. We explore the use of effective potentials based on the Feynman path centroid variable in order to simulate large quantum clusters at a reduced computational cost. This centroid can be viewed as the “most” classical variable of a quantum system. Earlier work has shown that one can use a pairwise centroid pseudo-potential to simulate the quantum dynamics of hydrogen in the bulk phase at 25 K and 14 K [Chem. Phys. Lett. 249, 231, (1996)]. Bulk hydrogen, however, freezes below 14 K, so we focus on hydrogen clusters and nanodroplets in the very low temperature regime in order to study their structural behaviours. The calculation of the effective centroid potential is addressed along with its use in the context of molecular dynamics simulations. The effective pseudo-potential of a cluster is temperature dependent and shares similar behaviour as that in the bulk phase. Centroid structural properties in three dimensional space are presented and compared to the results of reference path-integral Monte Carlo simulations. The centroid pseudo-potential approach yields a great reduction in computation cost. With large cluster sizes, the approximate pseudo-potential results are in agreement with the exact reference calculations. An approach to deconvolute centroid structural properties in order to obtain real space results for hydrogen clusters of a wide range of sizes is also presented. The extension of the approach to the treatment of confined hydrogen is discussed, and concluding remarks are presented.

This thesis presents i-PI, a new path integral molecular dynamics code designed to capture nuclear quantum effects in ab initio electronic structure calculations of condensed phase systems. This software has an implementation of estimators used to calculate a wide range of static and dynamical properties and of state-of-the-art techniques used to increase the computational efficiency of path integral simulations. i-PI has been designed in a highly modular fashion, to ensure that it is as simple as possible to develop and implement new algorithms to keep up with the research frontier, and so that users can take maximum advantage of the numerous electronic structure programs which are freely available without needing to rewrite large amounts of code. Among the functionality of the i-PI code is a novel integrator for constant pressure dynamics, which is used to investigate the properties of liquid water at 750 K and 10 GPa, and efficient estimators for the calculation of single particle momentum distri- butions, which are used to study the properties of solid and liquid ammonia. These show respectively that i-PI can be used to make predictions about systems which are both difficult to study experimentally and highly non-classical in nature, and that it can illustrate the relative advantages and disadvantages of different theoretical methods and their ability to reproduce experimental data.

The objective of this thesis is to reach theoretical understanding of the unusual relationship between charge-ordering and superconductivity in correlated-electron systems. The competition between these broken symmetries and magnetism in the cuprate high temperature superconductors has been extensively discussed, but exists also in many other correlated-electron superconductors, including quasi-two-dimensional organic charge-transfer solids. It has been suggested that the same attractive interaction is responsible for both charge-order and superconductivity. We propose that the specific interaction is the tendency in correlated-electron systems to form spin-singlet bonds, which is strongly enhanced at the commensurate carrier density p of ½ a charge carrier per site, characteristic of all superconducting charge-transfer solids. To probe superconductivity driven by electron correlations, a necessary condition is that electron-electron interactions enhance superconducting pair-pair correlations, relative to the non-interacting limit. We have performed state of the art numerical calculations on the two-dimensional Hubbard model on different triangular lattices, as well as other lattices corresponding to K-BEDT-TTF based organic charge transfer solids, for the complete range of carrier densities per site p (0 ≤ p ≤ 1). We have shown that pair-pair correlation for each cluster is enhanced by electron-electron interaction only for p ≃ 0.5, far away from the density range thought to be important for superconductivity. Although initial focus is on charge-transfer solids, the results of the research will impact the field of correlated electrons as a whole. We believe our calculations will provide fundamental and fresh insight to the theory of superconductivity in strongly correlated systems.

In 1948, Richard Feynman published the first paper on his new approach to non-relativistic quantum mechanics. Before Feynman's work there were two mathematical formulations of quantum mechanics. Schrödinger's formulation was based on PDE (the Schrödinger equation) and states representation by wave functions, so it was in the framework of analysis and differential equations. The other formulation was Heisenberg's matrix algebra. Initially, they were thought to be competing. The proponents of one claimed that the other was “ wrong. ” Within a couple of years, John von Neumann had proved that they are equivalent. Although Feynman's theory was not fundamentally new, it nonetheless offered an entirely fresh and different perspective: via a precise formulation of Bohr's correspondence principle, it made quantum mechanics similar to classical mechanics in a precise sense. In addition, Feynman's approach made it possible to explain physical experiments, and, via diagrams, link them directly to computations. What resulted was a very powerful device for computing energies and scattering amplitudes - the famous Feynman's diagrams. In his formulation, Feynman aimed at representing the solution to the non-relativistic Schrödinger equation in the form of an “ average ” over histories or paths of a particle. This solution is commonly known as the Feynman path integral. It plays an important role in the theory but appears as a postulate based on intuition coming from physics rather than a justified mathematical object. This is why Feynman's vision has caught the attention of many mathematicians as well as physicists. The papers of Gelfand, Cameron, and Nelson are among the first, and more substantial, attempts to supply Feynman's theory with a rigorous mathematical foundation. These attempts were followed by many others, but unfortunately all of them were not quite satisfactory. The difficulty comes from a need to define a measure on an infinite-dimensional space of continuous functions that represent all possible paths of a particle. This Feynman's measure has to produce an integral with the properties requested by Feynman. In particular, the expression for the Feynman measure has to involve the non-absolutely integrable Fresnel integrands. The non-absolute integrability of the Fresnel integrands makes the measure fail to be positive and to have the countably additive property. Thus, a well-defined measure in the case of the Feynman path integral does not exist. Extensive research has been done on the methods of relating the Feynman path integral to the integral with respect to the Wiener measure. The method of analytic continuation in mass defines the Feynman path integral as a certain limit of the Wiener integrals. Unfortunately, this method can be used as definition for only almost all values of the mass parameter in the Schrödinger equation. For physicists, this is not a satisfactory result and needs to be improved. In this work we examine those questions which originally led to the Feynman path integral. By now we know that Feynman's “ dream ” cannot be realized as a positive and countably additive measure on the path-space. Here, we offer a new way out by modifying Feynman's question, and thereby achieving a solution to the Schrödinger equation via a different kind of averages in the path-space. We give our version of the question that Feynman “ should have asked ” in order to realize the elusive path integral. In our formulation, we get a Feynman path integral as a limit of linear functionals, as opposed to the more familiar inductive limits of positive measures, traditionally used for constructing the Wiener measure, and related Gaussian families. We adapt here an approach pioneered by Patrick Muldowney. In it, Muldowney suggested a Henstock integration technique in order to deal with the non-absolute integrability of the kind of Fresnel integrals which we need in our solution to Feynman's question. By applying Henstock's theory to Fresnel integrals, we construct a complex-valued “ probability distribution functions ” on the path-space. Then we use this “ probability ” distribution function to define the Feynman path integral as an inductive limit. This establishes a mathematically rigorous Feynman limit, and at the same time, preserves Feynman's intuitive idea in resulting functional. In addition, our definition, and our solution, do not place any restrictions on any of the parameters in the Schrödinger equation, and have a potential to offer useful computational experiments, and other theoretical insights.

abstract: I describe the first continuous space nuclear path integral quantum Monte Carlo method, and calculate the ground state properties of light nuclei including Deuteron, Triton, Helium-3 and Helium-4, using both local chiral interaction up to next-to-next-to-leading-order and the Argonne $v_6'$ interaction. Compared with diffusion based quantum Monte Carlo methods such as Green's function Monte Carlo and auxiliary field diffusion Monte Carlo, path integral quantum Monte Carlo has the advantage that it can directly calculate the expectation value of operators without tradeoff, whether they commute with the Hamiltonian or not. For operators that commute with the Hamiltonian, e.g., the Hamiltonian itself, the path integral quantum Monte Carlo light-nuclei results agree with Green's function Monte Carlo and auxiliary field diffusion Monte Carlo results. For other operator expectations which are important to understand nuclear measurements but do not commute with the Hamiltonian and therefore cannot be accurately calculated by diffusion based quantum Monte Carlo methods without tradeoff, the path integral quantum Monte Carlo method gives reliable results. I show root-mean-square radii, one-particle number density distributions, and Euclidean response functions for single-nucleon couplings. I also systematically describe all the sampling algorithms used in this work, the strategies to make the computation efficient, the error estimations, and the details of the implementation of the code to perform calculations. This work can serve as a benchmark test for future calculations of larger nuclei or finite temperature nuclear matter using path integral quantum Monte Carlo. / Dissertation/Thesis / Doctoral Dissertation Physics 2020

An exact quantum Monte Carlo algorithm for interacting particles in the spatial continuum is extended to exploit the massive parallelism offered by graphics processing units. Its efficacy is tested on the Calogero-Sutherland model describing a system of bosons interacting in one spatial dimension via an inverse square law. Due to the long range nature of the interactions, this model has proved difficult to simulate via conventional path integral Monte Carlo methods running on conventional processors. Using Graphics Processing Units, optimal speedup factors of up to 640 times are obtained for N = 126 particles. The known results for the ground state energy are confirmed and, for the first time, the effects of thermal fluctuations at finite temperature are explored.