Variational Monte Carlo Calculations Research Articles

Efficient calculation of unbiased atomic forces in ab initio variational Monte Carlo

quantum Monte Carlo (QMC) is a state-of-the-art numerical approach for evaluating accurate expectation values of many-body wave functions. However, one of the major drawbacks that still hinders widespread QMC applications is the lack of an affordable scheme to compute unbiased atomic forces. In this study, we propose an efficient method to obtain unbiased atomic forces and pressures in the variational Monte Carlo (VMC) framework with the Jastrow-correlated Slater determinant ansatz or the Jastrow antisymmetrized geminal power ansatz, exploiting the gauge-invariant and locality properties of their geminal representation. We demonstrate the effectiveness of our method for H2 and Cl2 molecules and for the cubic boron nitride crystal. Our framework has a better algorithmic scaling with the system size than the traditional finite-difference method and, in practical applications, is as efficient as single-point VMC calculations. Thus, it paves the way to study dynamical properties of materials, such as phonons, and is beneficial for pursuing more reliable machine-learning interatomic potentials based on unbiased VMC forces. Published by the American Physical Society 2024

Finding the Dynamics of an Integrable Quantum Many‐Body System via Machine Learning

AbstractThe dynamics of the Gaudin magnet (“central‐spin model”) is studied using machine‐learning methods. This model is of practical importance, for example, for studying non‐Markovian decoherence dynamics of a central spin interacting with a large bath of environmental spins and for studies of nonequilibrium superconductivity. The Gaudin magnet is also integrable, admitting many conserved quantities. Machine‐learning methods may be well suited to exploiting the high degree of symmetry in integrable problems, even when an explicit analytic solution is not obvious. Motivated in part by this intuition, a neural‐network representation (restricted Boltzmann machine) is used for each variational eigenstate of the model Hamiltonian. Accurate representations of the ground state and of the low‐lying excited states of the Gaudin‐magnet Hamiltonian are then obtained through a variational Monte Carlo calculation. From the low‐lying eigenstates, the non‐perturbative dynamic transverse spin susceptibility is found, describing the linear response of a central spin to a time‐varying transverse magnetic field in the presence of a spin bath. Having an efficient description of this susceptibility opens the door to improved characterization and quantum control procedures for qubits interacting with an environment of quantum two‐level systems.

Scalable neural quantum states architecture for quantum chemistry

Variational optimization of neural-network representations of quantum states has been successfully applied to solve interacting fermionic problems. Despite rapid developments, significant scalability challenges arise when considering molecules of large scale, which correspond to non-locally interacting quantum spin Hamiltonians consisting of sums of thousands or even millions of Pauli operators. In this work, we introduce scalable parallelization strategies to improve neural-network-based variational quantum Monte Carlo calculations for ab-initio quantum chemistry applications. We establish GPU-supported local energy parallelism to compute the optimization objective for Hamiltonians of potentially complex molecules. Using autoregressive sampling techniques, we demonstrate systematic improvement in wall-clock timings required to achieve coupled cluster with up to double excitations baseline target energies. The performance is further enhanced by accommodating the structure of resultant spin Hamiltonians into the autoregressive sampling ordering. The algorithm achieves promising performance in comparison with the classical approximate methods and exhibits both running time and scalability advantages over existing neural-network based methods.

Understanding and eliminating spurious modes in variational Monte Carlo using collective variables

The use of neural network parametrizations to represent the ground state in variational Monte Carlo (VMC) calculations has generated intense interest in recent years. However, as we demonstrate in the context of the periodic Heisenberg spin chain, this approach can produce unreliable wave function approximations. One of the most obvious signs of failure is the occurrence of random, persistent spikes in the energy estimate during training. These energy spikes are caused by regions of configuration space that are over-represented by the wave function density, which are called ``spurious modes'' in the machine learning literature. After exploring these spurious modes in detail, we demonstrate that a collective-variable-based penalization yields a substantially more robust training procedure, preventing the formation of spurious modes and improving the accuracy of energy estimates. Because the penalization scheme is cheap to implement and is not specific to the particular model studied here, it can be extended to other applications of VMC where a reasonable choice of collective variable is available.

Probing spin-isospin excitations in proton-rich nuclei via theC11(p,n)N11reaction

Tracking the evolution of nuclear properties away from stability serves as a valuable test for nuclear models. In the present work, the $(p,n)$ charge-exchange reaction was used to test the extraction of ${\ensuremath{\beta}}^{\ensuremath{-}}$ Gamow-Teller transition strengths, $B(\mathrm{GT})$, from proton-rich unstable isotopes, and the resulting $B(\mathrm{GT})$ values were compared to shell-model and ab initio calculations. The $^{11}\mathrm{C}(p,n)^{11}\mathrm{N}$ reaction was measured in inverse kinematics at 95 MeV/u at the National Superconducting Cyclotron Laboratory. The $B(\mathrm{GT})$ values to the ${\frac{1}{2}}^{\ensuremath{-}}$ state at 0.73 MeV and the ${\frac{3}{2}}^{\ensuremath{-}}$ state at 2.86 MeV in $^{11}\mathrm{N}$ were determined to be $0.18{(1)}^{\mathrm{stat}}{(3)}^{\mathrm{sys}}$ and $0.18{(1)}^{\mathrm{stat}}{(4)}^{\mathrm{sys}}$, respectively. These results are consistent with shell-model calculations using the wbp interaction after introducing a phenomenological quenching factor and with ab initio variational Monte Carlo calculations using the $NV2+3I{a}^{*}$ $NN$ and $3N$ interactions without any scaling. Additionally, this result is consistent with the $B(\mathrm{GT})$ values extracted from mirror $^{11}\mathrm{B}(n,p)$ and $^{11}\mathrm{B}(t,^{3}\mathrm{He})$ reactions. This experiment demonstrates the feasibility of using the $(p,n)$ probe in inverse kinematics to extract $B(\mathrm{GT})$ from proton-rich nuclei, although improved background suppression will be important in future experiments.

Mottness induced superfluid phase fluctuation with increased density

Recent observation of diminishing superfluid phase stiffness upon increasing carrier density in cuprate high-temperature superconductors is unexpected from the quantum density-phase conjugation of superfluidity. Here, through analytic estimation and verified via variational Monte Carlo calculation of an emergent Bose liquid, we point out that Mottness of the underlying carriers can cause a stronger phase fluctuation of the superfluid with increasing carrier density. This effect turns the expected density-increased phase stiffness into a dome shape, in good agreement with the recent observation. Specifically, the effective mass divergence due to ‘jamming’ of the low-energy bosons reproduces the observed nonlinear relation between phase stiffness and transition temperature. Our results suggest a new paradigm, in which unconventional superconductivity in some strongly correlated materials is described by physics of bosonic superfluidity, as opposed to pairing-strength limited Cooper pairing.

Weighted nodal domain averages of eigenstates for quantum Monte Carlo and beyond

We study the nodal properties of many-body eigenstates of stationary Schr\"odinger equation that affect the accuracy of real-space quantum Monte Carlo calculations. In particular, we introduce weighted nodal domain averages that provide a new probe of nodal surfaces beyond the usual expectations. Particular choices for the weight function reveal, for example, that the difference between two arbitrary fermionic eigenvalues is given by the nodal hypersurface integrals normalized by overlaps with the bosonic ground state of the given Hamiltonian. Noninteracting and fully interacting Be atom with corresponding almost exact and approximate wave functions are used to illustrate several aspects of these concepts. Variational formulations that employ different weights are proposed for prospective improvement of nodes in variational and fixed-node diffusion Monte Carlo calculations.

Atomic shell structure from Born probabilities: Comparison to other shell descriptors and persistence in molecules.

Real space chemical bonding descriptors, such as the electron localization function or the Laplacian of the electron density, have been widely used in electronic structure theory thanks to their power to provide chemically intuitive spatial images of bonded and non-bonded interactions. This capacity stems from their ability to display the shell structure of atoms and its distortion upon molecular formation. Here, we examine the spatial position of the N electrons of an atom at the maximum of the square of the wavefunction, the so-called Born maximum, as a shell structure descriptor for ground state atoms with Z = 1-36, comparing it to other available indices. The maximization is performed with the help of variational quantum Monte Carlo calculations. We show that many electron effects (mainly Pauli driven) are non-negligible, that Born shells are closer to the nucleus than any other of the examined descriptors, and that these shells are very well preserved in simple molecules.

Two-Hole Ground State: Dichotomy in Pairing Symmetry

A single-hole ground state Ansatz for the two-dimensional t-J model has been recently studied by the variational Monte Carlo (VMC) method. Such a doped hole behaves like a "twisted" non-Landau quasiparticle characterized by an emergent quantum number in agreement with exact numerics. In this work, we further investigate the ground state of two holes by VMC. It is found that the two holes strongly attract each other to form a pairing state with a new quantum number the same as obtained by the numerical exact diagonalization and density matrix renormalization group (DMRG) calculations. A unique feature of this pairing state is a dichotomy in the pairing symmetry, i.e., a d-wave in terms of the electron c operators and an s-wave in terms of the new quasiparticles, as explicitly illustrated in the ground state wave function. A similar VMC study of a two-hole wave function for the t-J two-leg ladder also yields a good agreement with the DMRG result. We demonstrate that the pairing mechanism responsible for the strong binding here is not due to the long-range antiferromagnetic order nor the resonating-valence-bound pairing in the spin background but is the consequence of the quantum phase-strings created by the hopping of holes. The resulting spin-current pattern mediating the pairing force is explicitly illustrated in the VMC calculation. Physical implications to superconductivity at finite doping are also discussed.

Mirror nucleon removal reactions in p -shell nuclei

Nucleon removal reactions have been shown to be an effective tool for studying the single particle structure of nuclei. This work continues efforts to experimentally probe and benchmark the reaction and structure models used to calculate the removal reaction cross sections when using microscopic nuclear structure inputs. Three different single nucleon removal reactions were performed, from p-shell nuclei with masses A=7, 9, and 10. The residual nuclei from the reactions were detected in coincidence with γ rays to determine partial cross sections to individual final states. The eikonal direct-reaction model is combined with overlap functions and residual nucleus densities from microscopic, variational Monte Carlo calculations to provide consistent nuclear structure input to the partial cross section calculations. Comparisons of measured and calculated cross sections, including for mirror reactions, are presented. The analysis of the partial cross sections leading to the ground states shows a similar behavior to the one observed from analyses of inclusive cross sections using shell model nuclear structure input: the theoretical description of the removal process is in better agreement with the data when removing weakly bound nucleons, than when removing well-bound ones. The two mirror reaction pairs presented here show consistent results between the respective members of the pairs. The results obtained for the population of the excited states, however, show a systematically different trend that appears connected to the structure part of the calculation. Additional cases are needed to better understand the respective roles of structure and dynamical effects in the deviations.1 MoreReceived 24 November 2021Accepted 18 February 2022DOI:https://doi.org/10.1103/PhysRevC.105.034314©2022 American Physical SocietyPhysics Subject Headings (PhySH)Research AreasDirect reactionsProperties6 ≤ A ≤ 19TechniquesNuclear reactionsNuclear structure & decaysQuantum Monte CarloSpectrometers & spectroscopic techniquesNuclear Physics

Magnon condensation in dimerized antiferromagnets with spin-orbit coupling

Bose-Einstein condensation (BEC) of triplet excitations triggered by a magnetic field, sometimes called magnon BEC, in dimerized antiferromagnets gives rise to a long-range antiferromagnetic order in the plane perpendicular to the applied magnetic field. To explore the effects of spin-orbit coupling on magnon condensation, we study a spin model on a distorted honeycomb lattice with dimerized Heisenberg exchange ($J$ terms) and uniform off-diagonal exchange ($\Gamma'$ terms) interactions. Via variational Monte Carlo calculations and spin-wave theory, we find that an out-of-plane magnetic field can induce different types of long-range magnetic orders, no matter if the ground state is a non-magnetic dimerized state or an ordered N\'{e}el state. Furthermore, the critical properties of field-driven phase transitions in the presence of spin-orbit couplings, as illustrated from spin-wave spectrum and interpreted by effective field theory, can be different from the conventional magnon BEC. Our study is helpful to understand the rich phases of spin-orbit coupled antiferromagnets induced by magnetic fields.

Dimerization tendencies of the pyrochlore Heisenberg antiferromagnet: A functional renormalization group perspective

We investigate the ground state properties of the spin-$1/2$ pyrochlore Heisenberg antiferromagnet using pseudofermion functional renormalization group techniques. The first part of our analysis is based on an enhanced parton mean-field approach which takes into account fluctuation effects from renormalized vertex functions. Our implementation of this technique extends earlier approaches and resolves technical difficulties associated with a diagrammatic overcounting. Using various parton ans\"atze for quantum spin liquids, dimerized and nematic states our results indicate a tendency for lattice symmetry breaking in the ground state. While overall quantum spin liquids seem unfavorable in this system, the recently proposed monopole state still shows the strongest support among all spin liquid ans\"atze that we have tested, which is further confirmed by our complementary variational Monte Carlo calculations. In the second part of our investigation, we probe lattice symmetry breaking more directly by applying the pseudofermion functional renormalization group to perturbed systems. Our results from this technique confirm that the system's ground state either exhibits broken $C_3$ rotation symmetry, or a combination of inversion and $C_3$ symmetry breaking.

Spin texture in doped Mott insulators with spin-orbit coupling

A hole injected into a Mott insulator will gain an internal structure as recently identified by exact numerics, which is characterized by a nontrivial quantum number whose nature is of central importance in understanding the Mott physics. In this work, we show that a spin texture associated with such an internal degree of freedom can explicitly manifest after the spin degeneracy is lifted by a \emph{weak} Rashba spin-orbit coupling (SOC). It is described by an emergent angular momentum $J_{z}=\pm3/2$ as shown by both exact diagonalization (ED) and variational Monte Carlo (VMC) calculations, which are in good agreement with each other at a finite size. In particular, as the internal structure such a spin texture is generally present in the hole composite even at high excited energies, such that a corresponding texture in momentum space, extending deep inside the Brillouin zone, can be directly probed by the spin-polarized angle-resolved photoemission spectroscopy (ARPES). This is in contrast to a Landau quasiparticle under the SOC, in which the spin texture induced by SOC will not be protected once the excited energy is larger than the weak SOC coupling strength, away from the Fermi energy. We point out that the spin texture due to the SOC should be monotonically enhanced 1with reducing spin-spin correlation length in the superconducting/pseudogap phase at finite doping. A brief discussion of a recent experiment of the spin-polarized ARPES will be made.

The three-center two-positron bond.

Computational studies have shown that one or more positrons can stabilize two repelling atomic anions through the formation of two-center positronic bonds. In the present work, we study the energetic stability of a system containing two positrons and three hydride anions, namely 2e+[H3 3-]. To this aim, we performed a preliminary scan of the potential energy surface of the system with both electrons and positrons in a spin singlet state, with a multi-component MP2 method, that was further refined with variational and diffusion Monte Carlo calculations, and confirmed an equilibrium geometry with D 3h symmetry. The local stability of 2e+[H3 3-] is demonstrated by analyzing the vertical detachment and adiabatic energy dissociation channels. Bonding properties of the positronic compound, such as the equilibrium interatomic distances, force constants, dissociation energies, and bonding densities are compared with those of the purely electronic H3 + and Li3 + systems. Through this analysis, we find compelling similarities between the 2e+[H3 3-] compound and the trilithium cation. Our results strongly point out the formation of a non-electronic three-center two-positron bond, analogous to the well-known three-center two-electron counterparts, which is fundamentally distinct from the two-center two-positron bond [D. Bressanini, J. Chem. Phys., 2021, 155, 054306], thus extending the concept of positron bonded molecules.

Quantitative electron-electron interaction using local field factors from quantum Monte Carlo calculations

The effective electron-electron interaction in electron gas depends on both the density and spin local field factors. Variational diagrammatic quantum Monte Carlo calculations of the spin local field factor are reported. These are used together with the charge local field factor from previous diffusion quantum Monte Carlo calculations to quantitatively present the full effective spin-dependent electron-electron interaction in three-dimensional electron gas. Very simple quadratic formulas are presented for the local field factors that quantitatively produce all of the response functions of the electron gas at metallic densities. Exchange and correlation become increasingly important at low densities. At the compressibility divergence at ${r}_{s}=5.25$, both the direct (screened Coulomb) term and the charge-dependent exchange term in the electron-electron interaction at $q=0$ are separately divergent. However, due to large cancellations, their difference is finite, well behaved, and much smaller than either term separately. As a result, the spin contribution to the electron-electron interaction becomes an important factor. The static electron-electron interaction is repulsive as a function of density but is less repulsive for electrons with parallel spins. The effect of allowing a deformable, rather than rigid, positive background is shown to be as quantitatively important as exchange and correlation. As a simple concrete example, the electron-electron interaction is calculated using the measured bulk modulus of the alkali metals with a linear phonon dispersion. The net electron-electron interaction in lithium is attractive for wave vectors $0\ensuremath{-}2{k}_{F}$, which suggests superconductivity, and is mostly repulsive for the other alkali metals.

Neural-Network Quantum States for Spin-1 Systems: Spin-Basis and Parameterization Effects on Compactness of Representations.

Neural network quantum states (NQS) have been widely applied to spin-1/2 systems, where they have proven to be highly effective. The application to systems with larger on-site dimension, such as spin-1 or bosonic systems, has been explored less and predominantly using spin-1/2 Restricted Boltzmann Machines (RBMs) with a one-hot/unary encoding. Here, we propose a more direct generalization of RBMs for spin-1 that retains the key properties of the standard spin-1/2 RBM, specifically trivial product states representations, labeling freedom for the visible variables and gauge equivalence to the tensor network formulation. To test this new approach, we present variational Monte Carlo (VMC) calculations for the spin-1 anti-ferromagnetic Heisenberg (AFH) model and benchmark it against the one-hot/unary encoded RBM demonstrating that it achieves the same accuracy with substantially fewer variational parameters. Furthermore, we investigate how the hidden unit complexity of NQS depend on the local single-spin basis used. Exploiting the tensor network version of our RBM we construct an analytic NQS representation of the Affleck-Kennedy-Lieb-Tasaki (AKLT) state in the spin-1 basis using only hidden units, compared to required in the basis. Additional VMC calculations provide strong evidence that the AKLT state in fact possesses an exact compact NQS representation in the basis with only hidden units. These insights help to further unravel how to most effectively adapt the NQS framework for more complex quantum systems.

Confined atoms in plasma environment: variational Monte Carlo calculations

Hydrogen (H) and Helium (He) atoms restricted by an impenetrable spherical box within plasma environment sight are investigated. The effect of compression and the presence of the plasma environment on the energy of H and He in the ground state is investigated. The plasma effect is considered by utilising Debye screening potential. The Schrödinger equation is solved using the variational Monte Carlo method with a compact trial wave function depending on many variational parameters. Our results are compared with the most recent accurate values. The obtained results are in agreement with the latest results. These results could be extended to incorporate He-like ions up to Z = 10 with good precision.

First-principles quantum Monte Carlo studies for prediction of double minima for positronic hydrogen molecular dianion.

We studied the positron (e+) interaction with the hydrogen molecular dianion H2 2- to form the positronic bound state of [H-; e+; H-] using the first-principles quantum Monte Carlo method combined with the multi-component molecular orbital one. H2 2- itself is unstable, but it was shown that such an unbound H2 2- may become stable by intermediating a positron and forming the positronic covalent bond of the [H-; e+; H-] system [J. Charry et al., Angew. Chem., Int. Ed. 57, 8859-8864 (2018)]. We newly found that [H-; e+; H-] has double minima containing another positronic bound state of [H2; Ps-]-like configuration with the positronium negative ion Ps- at the bond distance approximately equal to the equilibrium H2 molecule. Our multi-component variational Monte Carlo calculation and the multi-component configuration interaction one resulted in the positronic covalent bonded structure being the global minimum, whereas a more sophisticated multi-component diffusion Monte Carlo calculation clearly showed that the [H2; Ps-]-like structure at the short bond distance is energetically more stable than the positronic covalent bonded one. The relaxation due to interparticle correlation effects pertinent to Ps- (or Ps) formation is crucial for the formation of the Ps-A2-like structure for binding a positron to the non-polar negatively charged dihydrogen.

Efficient local energy evaluation for multi-Slater wave functions in orbital space quantum Monte Carlo.

We present an algorithm for calculating the local energy of a multi-Slater wave function in orbital space quantum Monte Carlo (QMC). Recent developments in selected configuration interaction methods have led to increased interest in using multi-Slater trial wave functions in various QMC methods. For an ab initio Hamiltonian, our algorithm has a cost scaling of O(n5 + nc), as opposed to the O(n4nc) scaling of existing orbital space algorithms, where n is the system size and nc is the number of configurations in the wave function. We present our method using variational Monte Carlo calculations with the Jastrow multi-Slater wave function, although the formalism should be applicable for auxiliary field QMC. We apply it to polyacetylene and demonstrate the possibility of using a much larger number of configurations than possible using existing methods.

Magnetic and spin-liquid phases in the frustrated t−t′ Hubbard model on the triangular lattice

The Hubbard model and its strong-coupling version, the Heisenberg one, have been widely studied on the triangular lattice to capture the essential low-temperature properties of different materials. One example is given by transition metal dichalcogenides, as 1T$-$TaS$_2$, where a large unit cell with $13$ Ta atom forms weakly-coupled layers with an isotropic triangular lattice. By using accurate variational Monte Carlo calculations, we report the phase diagram of the $t-t^\prime$ Hubbard model on the triangular lattice, highlighting the differences between positive and negative values of $t^\prime/t$; this result can be captured only by including the charge fluctuations that are always present for a finite electron-electron repulsion. Two spin-liquid regions are detected: one for $t^\prime/t<0$, which persists down to intermediate values of the electron-electron repulsion, and a narrower one for $t^\prime/t>0$. The spin-liquid phase appears to be gapless, though the variational wave function has a nematic character, in contrast to the Heisenberg limit. We do not find any evidence for non-magnetic Mott phases in the proximity of the metal-insulator transition, at variance with the predictions (mainly based upon strong-coupling expansions in $t/U$) that suggest the existence of a weak-Mott phase that intrudes between the metal and the magnetically ordered insulator.