arXiv subjects

M. Chandler Bennett

Publications and source records attributed to M. Chandler Bennett.

17 recordsLinked to original sources

arXiv2023

Locality Error Free Effective Core Potentials for 3d Transition Metal Elements Developed for the Diffusion Monte Carlo Method

Pseudopotential locality errors have hampered the applications of the diffusion Monte Carlo (DMC) method in materials containing transition metals, in particular oxides. We have developed locality error free effective core potentials, pseudo-Hamiltonians, for transition metals ranging from Cr to Zn. We have modified a procedure published by some of us in [M.C. Bennett et al, JCTC 18 (2022)]. We carefully optimized our pseudo-Hamiltonians and achieved transferability errors comparable to the best semilocal pseudopotentials used with DMC but without incurring in locality errors. Our pseudo-Hamiltonian set (named OPH23) bears the potential to significantly improve the accuracy of many-body-first-principles calculations in fundamental science research of complex materials involving transition metals.

cond-mat.mtrl-sci↗

arXiv2022

Magnetic measures of purity for MnBi$_2$Te$_4$

The intrinsically anti-ferromagnetic topological insulator, MnBi$_2$Te$_4$ (MBT), has garnered significant attention recently. The excitement for this layered van der Waals bonded compound stems from its potential to host numerous exotic topological quantum states. For instance, quantum anomalous Hall states are predicted for odd-layer compounds and axion insulator states for the even-layer compounds. Unfortunately, the realization of these phenomena has been hindered by experimental challenges such as the existence of negative charge carriers, i.e., electron doping, which have been linked to anti-site defects among the Mn and Bi sub-lattices. Based on high level diffusion Monte Carlo (DMC) and DMC-tuned DFT+U calculations, we provide benchmark quality results for the bulk Mn magnetization as well as for Mn$_{Bi}$ and Bi$_{Mn}$ defects. We use this information to refine and extend models that estimate the anti-site defect concentration in actual MBT samples when combined with data from magnetic susceptibility and intermediate field magnetization measurements. Our models are validated through favorable comparison with prior experimental studies that obtained both magnetic and site occupancy data. We then extend our estimates to a larger set of prior samples to identify a probable zone of low defect density that has yet to be reached in synthesis. We anticipate our theoretically based magnetic purity measures may be used as minimization targets in the cycle of refinement needed to synthesize MBT samples with low anti-site defect concentrations and more reproducible topological properties.

cond-mat.mtrl-sci↗

arXiv2022

A new generation of effective core potentials from correlated and spin-orbit calculations: selected heavy elements

We introduce new correlation consistent effective core potentials (ccECPs) for the elements I, Te, Bi, Ag, Au, Pd, Ir, Mo, and W with $4d$, $5d$, $6s$ and $6p$ valence spaces. These ccECPs are given as a sum of spin-orbit averaged relativistic effective potential (AREP) and effective spin-orbit (SO) terms. The construction involves several steps with increasing refinements from more simple to fully correlated methods. The optimizations are carried out with objective functions that include weighted many-body atomic spectra, norm-conservation criteria, and spin-orbit splittings. Transferability tests involve molecular binding curves of corresponding hydride and oxide dimers. The constructed ccECPs are systematically better and in a few cases on par with previous effective core potential (ECP) tables on all tested criteria and provide a significant increase in accuracy for valence-only calculations with these elements. Our study confirms the importance of the AREP part in determining the overall quality of the ECP even in the presence of sizable spin-orbit effects. The subsequent quantum Monte Carlo (QMC) calculations point out the importance of accurate trial wave functions which in some cases (mid series transition elements) require treatment well beyond single-reference.

cond-mat.mtrl-sci↗

arXiv2022

Origin of Metal-Insulator Transitions in Correlated Perovskite Metals

The mechanisms that drive metal-to-insulator transitions (MIT) in correlated solids are not fully understood. For example, the perovskite (PV) SrCoO3 is a FM metal while the oxygen-deficient (n-doped) brownmillerite (BM) SrCoO2.5 is an anti-ferromagnetic (AFM) insulator. Given the magnetic and structural transitions that accompany the MIT, the driver for such a MIT transition is unclear. We also observe that the perovskite metals LaNiO3, SrFeO3, and SrCoO3 also undergo MIT when n-doped via high-to-low valence compositional changes. Also, pressurizing the insulating BM SrCoO2.5 phase, drives a gap closing. Using DFT and correlated diffusion Monte Carlo approaches we demonstrate that the ABO3 perovskites most prone to MIT are self hole-doped materials, reminiscent of a negative charge-transfer system. Upon n-doping away from the negative-charge transfer metallic phase, an underlying charge-lattice (or e-phonon) coupling drives the system to a bond-disproportionated gapped state, thereby achieving ligand hole passivation at certain sites only, leading to charge-disproportionated states. The size of the gap opened is correlated with the size of the hole-filling at these ligand sites. This suggests that the interactions driving the gap opening to realize a MIT even in correlated metals is the charge-transfer energy, but it couples with the underlying phonons to enable the transition to the insulating phase. Other orderings (magnetic, charge, etc.) driven by weaker interactions are secondary and may assist gap openings at small dopings, but its the charge-transfer energy that predominantly determines the bandgap, with a negative energy preferring the metallic phase. This n-doping can be achieved by modulations in stoichiometry or composition or pressure. Hence, controlling the amount of the ligand-hole is key in controlling MIT. We compare our predictions to experiments where possible.

cond-mat.mtrl-sci↗

arXiv2021

A Combined First Principles Study of the Structural, Magnetic, and Phonon Properties of Monolayer CrI$_{3}$

The first magnetic 2D material discovered, monolayer (ML) CrI$_3$, is particularly fascinating due to its ground state ferromagnetism. Yet, because monolayer materials are difficult to probe experimentally, much remains unresolved about ML CrI$_{3}$'s structural, electronic, and magnetic properties. Here, we leverage Density Functional Theory (DFT) and high-accuracy Diffusion Monte Carlo (DMC) simulations to predict lattice parameters, magnetic moments, and spin-phonon and spin-lattice coupling of ML CrI$_{3}$. We exploit a recently developed surrogate Hessian DMC line search technique to determine CrI$_{3}$'s monolayer geometry with DMC accuracy, yielding lattice parameters in good agreement with recently-published STM measurements - an accomplishment given the $\sim 10$% variability in previous DFT-derived estimates depending upon the functional. Strikingly, we find previous DFT predictions of ML CrI$_3$'s magnetic spin moments are correct on average across a unit cell, but miss critical local spatial fluctuations in the spin density revealed by more accurate DMC. DMC predicts magnetic moments in ML CrI$_3$ are 3.62 $μ_B$ per chromium and -0.145 $μ_B$ per iodine; both larger than previous DFT predictions. The large disparate moments together with the large spin-orbit coupling of CrI$_3$'s I-$\textit{p}$ orbital suggests a ligand superexchange-dominated magnetic anisotropy in ML CrI$_3$, corroborating recent observations of magnons in its 2D limit. We also find ML CrI$_3$ exhibits a substantial spin-phonon coupling of $\sim$3.32 cm$^{-1}$. Our work thus establishes many of ML CrI$_{3}$'s key properties, while also continuing to demonstrate the pivotal role DMC can assume in the study of magnetic and other 2D materials.

cond-mat.mtrl-sci↗

arXiv2021

Cohesion and excitations of diamond-structure silicon by quantum Monte Carlo: Benchmarks and control of systematic biases

We have carried out quantum Monte Carlo (QMC) calculations of silicon crystal focusing on the accuracy and systematic biases that affect the electronic structure characteristics. The results show that 64 and 216 atom supercells provide an excellent consistency for extrapolated energies per atom in the thermodynamic limit for ground, excited, and ionized states. We have calculated the ground state cohesion energy with both $\textit{systematic and statistical errors}$ below $\approx$0.05 eV. The ground state exhibits a fixed-node error of only $1.3(2)\%$ of the correlation energy, suggesting an unusually high accuracy of the corresponding single-reference trial wave function. We obtain a very good agreement between optical and quasiparticle gaps that affirms the marginal impact of excitonic effects. Our most accurate results for band gaps differ from the experiments by about 0.2 eV. This difference is assigned to a combination of residual finite-size and fixed-node errors. We have estimated the crystal Fermi level referenced to vacuum that enabled us to calculate the edges of valence and conduction bands in agreement with experiments.

cond-mat.mtrl-sci↗

arXiv2020

Towards a Systematic Improvement of the Fixed-Node Approximation in Diffusion Monte Carlo for Solids -- A Case Study In Diamond

While Diffusion Monte Carlo (DMC) is in principle an exact stochastic method for \textit{ab initio} electronic structure calculations, in practice the fermionic sign problem necessitates the use of the fixed-node approximation and trial wavefunctions with approximate nodes (or zeros) must be used. This approximation introduces a variational error in the energy that potentially can be tested and systematically improved. Here, we present a computational method that produces trial wavefunctions with systematically improvable nodes for DMC calculations of periodic solids. These trial wavefunctions are efficiently generated with the configuration interaction using a perturbative selection made iteratively (CIPSI) method. A simple protocol in which both exact and approximate results for finite supercells are used to extrapolate to the thermodynamic limit is introduced.

physics.chem-ph↗

arXiv2020

QMCPACK: Advances in the development, efficiency, and application of auxiliary field and real-space variational and diffusion Quantum Monte Carlo

We review recent advances in the capabilities of the open source ab initio Quantum Monte Carlo (QMC) package QMCPACK and the workflow tool Nexus used for greater efficiency and reproducibility. The auxiliary field QMC (AFQMC) implementation has been greatly expanded to include k-point symmetries, tensor-hypercontraction, and accelerated graphical processing unit (GPU) support. These scaling and memory reductions greatly increase the number of orbitals that can practically be included in AFQMC calculations, increasing accuracy. Advances in real space methods include techniques for accurate computation of band gaps and for systematically improving the nodal surface of ground state wavefunctions. Results of these calculations can be used to validate application of more approximate electronic structure methods including GW and density functional based techniques. To provide an improved foundation for these calculations we utilize a new set of correlation-consistent effective core potentials (pseudopotentials) that are more accurate than previous sets; these can also be applied in quantum-chemical and other many-body applications, not only QMC. These advances increase the efficiency, accuracy, and range of properties that can be studied in both molecules and materials with QMC and QMCPACK.

physics.comp-ph↗

arXiv2020

Accurate atomic correlation and total energies for correlation consistent effective core potentials

Very recently, we introduced a set of correlation consistent effective core potentials (ccECPs) constructed within full many-body approaches. By employing significantly more accurate correlated approaches we were able to reach a new level of accuracy for the resulting effective core Hamiltonians. We also strived for simplicity of use and easy transferability into a variety of electronic structure methods in quantum chemistry and condensed matter physics. Here, as a reference for future use, we present exact or nearly-exact total energy calculations for these ccECPs. The calculations cover H-Kr elements and are based on the state-of-the-art configuration interaction (CI), coupled-cluster (CC), and quantum Monte Carlo (QMC) calculations with systematically eliminated/improved errors. In particular, we carry out full CI/CCSD(T)/CCSDT(Q) calculations with cc-pVnZ with up to n=6 basis sets and we estimate the complete basis set limits. Using combinations of these approaches, we achieved an accuracy of $\approx$ 1-10 mHa for K-Zn atoms and $\approx$ 0.1-0.3 mHa for all other elements $-$ within about 1% or better of the ccECP total correlation energies. We also estimate the corresponding kinetic energies within the feasible limit of full CI calculations. In order to provide data for QMC calculations, we include fixed-node diffusion Monte Carlo energies for each element that give quantitative insights into the fixed-node biases for single-reference trial wave functions. The results offer a clear benchmark for future high accuracy calculations in a broad variety of correlated wave function methods such as CI and CC as well is in stochastic approaches such as real space sampling QMC.

cond-mat.mtrl-sci↗

arXiv2019

A new generation of effective core potentials from correlated calculations: 4s and 4p main group elements and first row additions

Recently, we developed a new method for generating effective core potentials (ECPs) using valence energy isospectrality with explicitly correlated all-electron (AE) excitations and norm-conservation criteria. We apply this methodology to the 3$^{rd}$-row main group elements, creating new correlation consistent effective core potentials (ccECPs) and also derive additional ECPs to complete the ccECP table for H-Kr. For K and Ca, we develop Ne-core ECPs and for the $4p$ main group elements, we construct [Ar]$3d^{10}$-core potentials. Scalar relativistic effects are included in their construction. Our ccECPs reproduce AE spectra with significantly better accuracy than many existing pseudopotentials and show better overall consistency across multiple properties. The transferability of ccECPs is tested on monohydride and monoxide molecules over a range of molecular geometries. For the constructed ccECPs we also provide optimized DZ - 6Z valence Gaussian basis sets.

cond-mat.mtrl-sci↗

arXiv2018

New generation of effective core potentials from correlated calculations: 2nd row elements

Very recently, we have introduced correlation consistent effective core potentials (ccECPs) derived from many-body approaches with the main target being its use in explicitly correlated methods but also in mainstream approaches. The ccECPs are based on reproducing excitation energies for a subset of valence states, i.e., achieving a near-isospectrality between the original and pseudo Hamiltonians. In addition, binding curves of dimer molecules have been used for refinement and overall improvement of transferability over a range of bond lengths. Here we apply similar ideas to the second row elements and study several aspects of the constructions in order to find the optimal (or nearly-optimal) solutions within the chosen ECP forms with $3s,3p$ valence space (Ne-core). New constructions exhibit accurate low-lying atomic excitations and equilibrium molecular bonds (on average within $\approx$ $0.03$ eV and $3$ mÅ), however, the errors for Al and Si oxide molecules at short bond lengths are notably larger for both ours and existing ECPs. Assuming this limitation, our ccECPs show a systematic balance between the criteria of atomic spectra accuracy and transferability for molecular bonds. In order to provide another option with much higher uniform accuracy, we also construct He-core ECPs for the whole row with typical discrepancies of $\approx$ 0.01 eV or smaller.

cond-mat.mtrl-sci↗

arXiv2018

New generation of effective core potentials from correlated calculations: 3d transition metal series

Recently, we have introduced a new generation of effective core potentials (ECPs) designed for accurate correlated calculations but equally useful for a broad variety of approaches. The guiding principle has been the isospectrality of all-electron and ECP Hamiltonians for a subset of valence many-body states using correlated, nearly-exact calculations. Here we present such ECPs for the 3d transition series Sc to Zn with Ne-core, i.e, with semi-core 3s and 3p electrons in the valence space. Besides genuine many-body accuracy, the operators are simple, being represented by a few gaussians per symmetry channel with resulting potentials that are bounded everywhere. The transferability is checked on selected molecular systems over a range of geometries. The ECPs show a high overall accuracy with valence spectral discrepancies typically $\approx$ 0.01-0.02 eV or better. They also reproduce binding curves of hydride and oxide molecules typically within 0.02-0.03 eV deviations over the full non-dissociation range of interatomic distances.

cond-mat.mtrl-sci↗

arXiv2018

QMCPACK : An open source ab initio Quantum Monte Carlo package for the electronic structure of atoms, molecules, and solids

QMCPACK is an open source quantum Monte Carlo package for ab-initio electronic structure calculations. It supports calculations of metallic and insulating solids, molecules, atoms, and some model Hamiltonians. Implemented real space quantum Monte Carlo algorithms include variational, diffusion, and reptation Monte Carlo. QMCPACK uses Slater-Jastrow type trial wave functions in conjunction with a sophisticated optimizer capable of optimizing tens of thousands of parameters. The orbital space auxiliary field quantum Monte Carlo method is also implemented, enabling cross validation between different highly accurate methods. The code is specifically optimized for calculations with large numbers of electrons on the latest high performance computing architectures, including multicore central processing unit (CPU) and graphical processing unit (GPU) systems. We detail the program's capabilities, outline its structure, and give examples of its use in current research calculations. The package is available at http://www.qmcpack.org .

physics.comp-ph↗

arXiv2017

A New Generation of Effective Core Potentials for Correlated Calculations

We outline ideas on desired properties for a new generation of effective core potentials (ECPs) that will allow valence-only calculations to reach the full potential offered by recent advances in many-body wave function methods. The key improvements include consistent use of correlated methods throughout ECP constructions and improved transferability as required for an accurate description of molecular systems over a range of geometries. The guiding principle is the isospectrality of all-electron and ECP Hamiltonians for a subset of valence states. We illustrate these concepts on a few first- and second-row atoms (B, C, N, O, S) and we obtain higher accuracy in transferability than previous constructions while using a semi-local ECPs with a small number of parameters. In addition, the constructed ECPs enable many-body calculations of valence properties with higher (or same) accuracy than their all-electron counterparts with uncorrelated cores. This implies that the ECPs include also some of the impacts of core-core and core-valence correlations on valence properties. The results open further prospects for ECP improvements and refinements.

physics.chem-ph↗

arXiv2017

Projector quantum Monte Carlo with averaged vs. explicit spin-orbit effects: applications to tungsten molecular systems

We present a recently developed projector quantum Monte Carlo method for calculations of electronic structure in systems with spin-orbit interactions. The method solves for many-body eigenstates in the presence of spin-orbit using the fixed-phase approximation.The trial wave function is built from two-component spinors and explicit Jastrow correlation factors while the core electrons are eliminated by relativistic effective core potentials with explicit spin-orbit terms. We apply this method to WO and W$_2$ molecules that enable us to build multi-reference wave functions and analyze in detail the impact of both electron correlations and of spin-orbit terms. These developments open new opportunities for calculations of systems with significant spin-orbit effects by many-body quantum Monte Carlo methods.

physics.chem-ph↗

arXiv2016

A Quantum Monte Carlo Study of mono(benzene)TM and bis(benzene)TM Systems

We present a study of mono(benzene)TM and bis(benzene)TM systems, where TM={Mo,W}. We calculate the binding energies by quantum Monte Carlo (QMC) approaches and compare the results with other methods and available experiments. The orbitals for the determinantal part of each trial wave function were generated from several types of DFT in order to optimize for fixed-node errors. We estimate and compare the size of the fixed-node errors for both the Mo and W systems with regard to the electron density and degree of localization in these systems. For the W systems we provide benchmarking results of the binding energies, given that experimental data is not available.

physics.chem-ph↗

arXiv2016

Quantum Monte Carlo with Variable Spins

We investigate the inclusion of variable spins in electronic structure quantum Monte Carlo, with a focus on diffusion Monte Carlo with Hamiltonians that include spin-orbit interactions. Following our previous introduction of fixed-phase spin-orbit diffusion Monte Carlo (FPSODMC), we thoroughly discuss the details of the method and elaborate upon its technicalities. We present a proof for an upper-bound property for complex nonlocal operators, which allows for the implementation of T-moves to ensure the variational property. We discuss the time step biases associated with our particular choice of spin representation. Applications of the method are also presented for atomic and molecular systems. We calculate the binding energies and geometry of the PbH and Sn$_2$ molecules, as well as the electron affinities of the 6$p$ row elements in close agreement with experiments.

physics.comp-ph↗