The numerical simulation of quantum many-body systems is an essential instrument in the research on condensed matter Physics. Recent years have witnessed remarkable progress in studying dynamical properties of non-relativistic Bose systems with quantum Monte Carlo (QMC) methods. On the other hand, the numerical study of Fermi systems is a still open problem of great relevance, as fermions constitute a substantial part of ordinary matter and methods for the accurate calculation of their ground-state and dynamical properties would be useful instruments for the interpretation of experimental data. In this thesis, a number of approximate schemes for studying ground-state and dynamical properties of quantum many-body systems are presented and employed to calculate ground-state and dynamical properties of Bose and Fermi systems. In particular, the Path Integral Ground State QMC method is used to investigate density fluctuations in one-dimensional systems of Helium atoms and hard rods, and the phaseless Auxiliary field QMC is used to investigate the electronic band and effective mass of the two-dimensional homogeneous electron gas.
The numerical simulation of quantum many-body systems is an essential instrument in the research on condensed matter Physics. Recent years have witnessed remarkable progress in studying dynamical properties of non-relativistic Bose systems with quantum Monte Carlo (QMC) methods. On the other hand, the numerical study of Fermi systems is a still open problem of great relevance, as fermions constitute a substantial part of ordinary matter and methods for the accurate calculation of their ground-state and dynamical properties would be useful instruments for the interpretation of experimental data. In this thesis, a number of approximate schemes for studying ground-state and dynamical properties of quantum many-body systems are presented and employed to calculate ground-state and dynamical properties of Bose and Fermi systems. In particular, the Path Integral Ground State QMC method is used to investigate density fluctuations in one-dimensional systems of Helium atoms and hard rods, and the phaseless Auxiliary field QMC is used to investigate the electronic band and effective mass of the two-dimensional homogeneous electron gas.
The study of strongly correlated quantum many-body systems is an outstanding challenge. Highly accurate results are needed for the understanding of practical and fundamental problems in condensed-matter physics, high energy physics, material science, quantum chemistry and so on. Our familiar mean-field or perturbative methods tend to be ineffective. Numerical simulations provide a promising approach for studying such systems. The fundamental difficulty of numerical simulation is that the dimension of the Hilbert space needed to describe interacting systems increases exponentially with the system size. Quantum Monte Carlo (QMC) methods are one of the best approaches to tackle the problem of enormous Hilbert space. They have been highly successful for boson systems and unfrustrated spin models. For systems with fermions, the exchange symmetry in general causes the infamous sign problem, making the statistical noise in the computed results grow exponentially with the system size. This hinders our understanding of interesting physics such as high-temperature superconductivity, metal-insulator phase transition. In this thesis, we present a variety of new developments in the auxiliary-field quantum Monte Carlo (AFQMC) methods, including the incorporation of symmetry in both the trial wave function and the projector, developing the constraint release method, using the force-bias to drastically improve the efficiency in Metropolis framework, identifying and solving the infinite variance problem, and sampling Hartree-Fock-Bogoliubov wave function. With these developments, some of the most challenging many-electron problems are now under control. We obtain an exact numerical solution of two-dimensional strongly interacting Fermi atomic gas, determine the ground state properties of the 2D Fermi gas with Rashba spin-orbit coupling, provide benchmark results for the ground state of the two-dimensional Hubbard model, and establish that the Hubbard model has a stripe order in the underdoped region.
Electronic structure quantum Monte Carlo Quantum Monte Carlo (QMC) is an advanced simulation methodology for studies of manybody quantum systems. The QMC approaches combine analytical insights with stochastic computational techniques for efficient solution of several classes of important many-body problems such as the stationary Schrödinger equation. QMC methods of various flavors have been applied to a great variety of systems spanning continuous and lattice quantum models, molecular and condensed systems, BEC-BCS ultracold condensates, nuclei, etc. In this review, we focus on the electronic structure QMC, i.e., methods relevant for systems described by the electron-ion Hamiltonians. Some of the key QMC achievements include direct treatment of electron correlation, accuracy in predicting energy differences and favorable scaling in the system size. Calculations of atoms, molecules, clusters and solids have demonstrated QMC applicability to real systems with hundreds of electrons while providing 90-95% of the correlation energy and energy differences typically within a few percent of experiments. Advances in accuracy beyond these limits are hampered by the so-called fixed-node approximation which is used to circumvent the notorious fermion sign problem. Many-body nodes of fermion states and their properties have therefore become one of the important topics for further progress in predictive power and efficiency of QMC calculations. Some of our recent results on the wave function nodes and related nodal domain topologies will be briefly reviewed. This includes analysis of few-electron systems and descriptions of exact and approximate nodes using transformations and projections of the highly-dimensional nodal hypersurfaces into the 3D space. Studies of fermion nodes offer new insights into topological properties of eigenstates such as explicit demonstrations that generic fermionic ground states exhibit the minimal number of two nodal domains. Recently proposed trial wave functions based on Pfaffians with pairing orbitals are presented and their nodal properties are tested in calculations of first row atoms and molecules. Finally, backflow "dressed" coordinates are introduced as another possibility for capturing correlation effects and for decreasing the fixed-node bias.
In this Thesis we will theoretically address some issues concerning the Physics of ultracold Fermi gases, all of them with experimental relevance. The field of ultracold gases, and more recently of ultracold Fermi gases, is gathering a lot of experimental and theoretical interest for two main reasons: the great control on the relevant parameters of the problem and the relative simplicity of the minimal theory which is able to correctly describe the system. Building upon this solid background, ultracold gases provided an ideal laboratory for testing more refined theories and also for addressing fundamental issues of quantum mechanics as well as for simulating more complex physical systems such as those encountered in condensed matter. Even if the effective hamiltonian of ultracold gases can be simple, due to the diluteness of the system and the low temperature, which imply low energy physics, the solution of the quantum mechanic equations governing the state of these systems is not always simple. For the static properties usually mean-field solutions exist or perturbative expansions can be produced in some regimes. However Quantum Monte Carlo (QMC) techniques provide more accurate results especially in the strongly interacting regimes. For confined systems it is possible to use QMC only for a few particles, so that, for large number of particles, a fruitful combined use of Density Functional Theory (DFT) and QMC is necessary. The study of the dynamics of ultracold gases has received little attention with QMC techniques, due to the intrinsic computational difficulty of the many-body problem, so that general hydrodynamic equations are often used for studying the propagation of smoothly varying perturbations. In this Thesis we use QMC techniques for studying the problem of ferromagnetism in repulsive or effectively repulsive ultracold gases without a lattice and the problem of the Bardeen-Cooper-Schrieffer to Bose-Einstein-Condensation (BCS-BEC) crossover in two dimensions. We use DFT in the Local Density Approximation (LDA) for calculating the density profiles of ultracold Fermi gases in harmonic magneto-optical traps, starting from QMC equations of state. We study the propagation of first and second sound in ultracold Fermi gases in cylindrical geometry, using the hydrodynamic equations of superfluids.
Variational and diffusion Monte Carlo (VMC and DMC) are widely used techniques in the Monte Carlo study of many-body quantum systems. Through efficient use of ran- dom sampling to solve many-dimensional integrals, they can be used to reliably solve the Schrödinger equation. Within the wider ecosystems of electronic structure calculation, quantum chemistry, and quantum simulation, quantum Monte Carlo (QMC) methods are used in tandem with density functional theory (DFT) and other computational methods to deliver insight into a vast array of condensed matter systems. Of particular interest to this work are systems in the intermediate correlation regime, where methods such as simple band theory and the Hubbard model break down. This thesis proposes and tests an explicit three-body backflow term to improve the accuracy of VMC and DMC calculations by incorporating higher-order correlation in order to reduce fixed-node er- ror in DMC, finding statistically significant improvements in ground state energies and improved variance in a water molecule. Then, QMC is used to calculate accurate charge densities for weak and intermediately correlated materials, to test commonly used dens- ity functional approximations in a controlled environment, providing insight into where these approximations perform well, and where they fail. Finally, DMC is used to generate ground state energy data for a dipolar Fermi gas of dressed Rydberg atoms interacting in the intermediate correlation regime. This data is parametrised in terms of interaction strength, for use in generating exchange-correlation functionals, to enable the DFT study of inhomogeneous systems of dressed Rydberg atoms.
Quantum Monte Carlo methods are a powerful suite of techniques for solving the quantum many-body problem. By using random numbers to stochastically sample quantum properties, QMC methods are capable of studying low-temperature quantum systems well beyond the reach of conventional deterministic techniques. QMC techniques have likewise been indispensible tools for augmenting our current knowledge of superfluidity and superconductivity. In this thesis, I present two new quantum Monte Carlo techniques, the Monte Carlo Power Method and Bose-Fermi Auxiliary-Field Quantum Monte Carlo, and apply previously developed Path Integral Monte Carlo methods to explore two new phases of quantum hard spheres and hydrogen. I lay the foundation for a subsequent description of my research by first reviewing the physics of quantum liquids in Chapter One and the mathematics behind Quantum Monte Carlo algorithms in Chapter Two. I then discuss the Monte Carlo Power Method, a stochastic way of computing the first several extremal eigenvalues of a matrix too memory-intensive to be stored and therefore diagonalized. As an illustration of the technique, I demonstrate how it can be used to determine the second eigenvalues of the transition matrices of several popular Monte Carlo algorithms. This information may be used to quantify how rapidly a Monte Carlo algorithm is converging to the equilibrium probability distribution it is sampling. I next present the Bose-Fermi Auxiliary-Field Quantum Monte Carlo algorithm. This algorithm generalizes the well-known Auxiliary-Field Quantum Monte Carlo algorithm for fermions to bosons and Bose-Fermi mixtures. Despite some shortcomings, the Bose-Fermi Auxiliary-Field Quantum Monte Carlo algorithm represents the first exact technique capable of studying Bose-Fermi mixtures of any size in any dimension. In Chapter Six, I describe a new Constant Stress Path Integral Monte Carlo algorithm for the study of quantum mechanical systems under high pressures. While the eventual hope is to apply this algorithm to the exploration of yet unidentified high-pressure, low-temperature phases of hydrogen, I employ this algorithm to determine whether or not quantum hard spheres can form a low-temperature bcc solid if exchange is not taken into account. In the final chapter of this thesis, I use Path Integral Monte Carlo once again to explore whether glassy para-hydrogen exhibits superfluidity. Physicists have long searched for ways to coax hydrogen into becoming a superfluid. I present evidence that, while glassy hydrogen does not crystallize at the temperatures at which hydrogen might become a superfluid, it nevertheless does not exhibit superfluidity. This is because the average binding energy per p-H2 molecule poses a severe barrier to exchange regardless of whether the system is crystalline. All in all, this work extends the reach of Quantum Monte Carlo methods to new systems and brings the power of existing methods to bear on new problems.
… a general method, suitable for electronic computing machines, of calculating the properties of any substance which may be considered as composed of interacting individual molecules. N. Metropolis et al. , 1953 Summary Quantum Monte Carlo methods have been very useful in providing exact results, or, at least, exact constraints on properties of electronic systems, in particular for the homogeneous electron gas. The results are, in many cases, more accurate than those from other quantum many-body methods, and provide unique capabilities and insights. In this chapter we introduce the general properties of stochastic methods and motivate their use on the quantum many-body problem. In particular, we discuss Markov chains and the computation of error estimates. The methods that we introduce in the next four chapters are quite different from those in Parts II and III: stochastic or quantum Monte Carlo methods. In stochastic methods, instead of solving deterministically for properties of the quantum many-body system, one sets up a random walk that samples for the properties. Historically the most important role of QMC for the electronic structure field has been to provide input into the other methods, most notably the QMC calculation of the HEG [109], used for the exchange– correlation functional in DFT. A second important role has been as benchmarks for other methods such asGW. There are systems for which QMC is uniquely suited, for example the Wigner transition in the low-density electron gas, see Sec. 3.1. In this chapter we introduce general properties of simulations, in particular Markov chains, and error estimates. In the following chapters we will apply this theory to three general classes of quantum Monte Carlo algorithms, namely variational (Ch. 23), projector (Ch. 24), and path-integral Monte Carlo (Ch. 25); Ch. 18 already introduced the QMC calculation of the impurity Green's function used in the dynamical mean-field method.We note that there are a variety of other QMC methods not covered in this book. Simulations First let us define what we mean by a simulation, since the word has other meanings in applied science. The dimensionality of phase space (i.e., the Hilbert space for a quantum system) is large or infinite. Even a classical system requires the positions and momenta of all particles, and, hence, the phase space for N classical particles has dimensionality 6 N .