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arXiv:2309.15262

Quantum Monte Carlo pair orbital wave functions for periodic systems towards the thermodynamical limit: ground states, excitations and spinors

Luboš Mitáš

Published Sep 26, 2023• 0 citations
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Abstract

We derive many-body single- and multi-reference wave functions for quantum Monte Carlo of periodic systems with an anti-symmetric portion that explicitly integrates over the Brillouin zone of one-particle Bloch states. The wave functions are BCS-like determinants for singlets and pfaffians for polarized states built with appropriate pair orbitals. This ab initio formalism is broadly applicable, eg, to description of quasi-particle band gaps, optical excitations and to systems with complicated Fermi surfaces. It generalizes to spin-dependent interactions using two-component spinor pairs.

DOI
10.48550/arxiv.2309.15262

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We derive many-body single- and multi-reference wave functions for quantum Monte Carlo of periodic systems with an anti-symmetric portion that explicitly integrates over the Brillouin zone of one-particle Bloch states. The wave functions are BCS-like determinants for singlets and pfaffians for polarized states built with appropriate pair orbitals. This ab initio formalism is broadly applicable, eg, to description of quasi-particle band gaps, optical excitations and to systems with complicated Fermi surfaces. It generalizes to spin-dependent interactions using two-component spinor pairs.
We derive many-body single and multireference wave functions for quantum Monte Carlo of periodic systems with an antisymmetric portion that explicitly integrates over the Brillouin zone of one-particle Bloch states. The wave functions are BCS-like determinants for singlets and Pfaffians for polarized states built with appropriate pair orbitals. This ab initio formalism is broadly applicable, e.g., to description of quasiparticle band gaps and optical excitations and to systems with complicated Fermi surfaces. It generalizes to spin-dependent interactions using two-component spinor pairs.
We discuss the importance of the fermion nodes for the quantum Monte Carlo (QMC) methods and find two cases of the exact nodes. We describe the structure of the generalized pairing wave functions in Pfaffian antisymmetric form and demonstrate their equivalency with certain class of configuration interaction wave functions. We present the QMC calculations of a model fermion system at unitary limit. We find the system to have the energy of E=0.425Efree and the condensate fraction of α=0.48. Further we also perform the QMC calculations of the potential energy surface and the electric dipole moment along that surface of the LiSr molecule. We estimate the vibrationally averaged dipole moment to be 〈D〉ν=0=−0.4(2).
The chapter describes the principles of how Quantum Monte Carlo (QMC) uses random numbers to compute properties of a non-relativistic quantum mechanical system. In a many-body system, this involves computation of multidimensional integrals, which can be very effectively calculated using Monte Carlo methods. The spin of particles will be added to this framework, along with identical particles as symmetric or antisymmetric wave functions. An introduction to orbitals follows, and a discussion of the characteristics of boson and fermion ground states.
The time-dependent quantum Monte Carlo method represents a many-electron state by an ensemble of replicas, in which each electron is described by a cloud of walkers which samples its density in physical space, one walker and one guide wave per replica, and it replaces the Hartree potential by a conditional interaction built from the walker positions. The sampling is in physical space rather than in configuration space, which keeps the cost polynomial. Here we derive that conditional interaction. Treating the walker as a localization of its electron to a finite resolution, we show that Bayes' theorem and a single empirical substitution yield the Nadaraya-Watson form which the method has used heuristically. The nonlocality length then becomes the width of the conditioning, and the pair and mean-field limits follow from one construction. Because the conditioning removes the gauge freedom which eliminates the orthonormality multipliers in Hartree-Fock, we enforce orthonormality by a term derived from the constraint. We generalize the formulation to spinors, where the Pauli suppression at coincidence becomes graded by the local spin alignment, and it reduces through the collinear and mean-field limits to the known two-particle spin equations. For two electrons in a double quantum dot in an inhomogeneous magnetic field, compared with the exact solution, the spinor equations reproduce the non-collinear spin geometry which collinear calculations cannot represent and recover the larger part of the entanglement missing from a single determinant. In the crossover between the exchange and the Zeeman regimes, where the singlet-triplet coherence sets the spin geometry, the replicas must carry that coherence themselves, as in the spin-coupled pair of valence-bond theory.
We present an approach for ab initio many-body calculations of excited states in solids. Using auxiliary-field quantum Monte Carlo, we introduce an orthogonalization constraint with virtual orbitals to prevent collapse of the stochastic Slater determinants in the imaginary-time propagation. Trial wave functions from density-functional calculations are used for the constraints. Detailed band structures can be calculated. Results for standard semiconductors are in good agreement with experiments; comparisons are also made with GW calculations and the connections and differences are discussed. For the challenging ZnO wurtzite structure, we obtain a fundamental band gap of 3.26(16) eV, consistent with experiments.
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.