Collective interlayer pairing and pair superfluidity in vertically stacked layers of dipolar excitons.

Layered bosonic dipolar fluids have been suggested to host a condensate of interlayer molecular bound states. However, experimental observation has remained elusive. Motivated by two recent experimental works [C. Hubert et al., Phys. Rev. X9, 021026 (2019) and D. J. Choksy et al., Phys. Rev. B 103, 045126 (2021)], we theoretically study, using numerically exact quantum Monte Carlo calculations, the experimental signatures of collective interlayer pairing in vertically stacked indirect exciton (IX) layers. We find that IX energy shifts associated with each layer evolve nontrivially as a function of density imbalance following a nonmonotonic trend with a jump discontinuity at density balance, identified with the interlayer IX molecule gap. This behavior discriminates between the superfluidity of interlayer bound pairs and independent dipole condensation in distinct layers. Considering finite temperature and finite density imbalance conditions, we find a cascade of Berezinskii-Kosterlitz-Thouless (BKT) transitions, initially into a pair superfluid and only then, at lower temperatures, into complete superfluidity of both layers. Our results may provide a theoretical interpretation of existing experimental observations in GaAs double quantum well (DQW) bilayer structures. Furthermore, to optimize the visibility of pairing dynamics in future studies, we present an analysis suggesting realistic experimental settings in GaAs and transition metal dichalcogenide (TMD) bilayer DQW heterostructures where collective interlayer pairing and pair superfluidity can be clearly observed.

Auxiliary field Quantum Monte Carlo for dilute neutrons on the lattice.

We employ constrained path Auxiliary Field Quantum Monte Carlo (AFQMC) in the pursuit of studying physical nuclear systems using a lattice formalism. Since AFQMC has been widely used in the study of condensed-matter systems such as the Hubbard model, we benchmark our method against published results for both one- and two-dimensional Hubbard model calculations. We then turn our attention to cold atomic and nuclear systems. We use an onsite contact interaction that can be tuned in order to reproduce the known scattering length and effective range of a given interaction. Developing this machinery allows us to extend our calculations to study nuclear systems within a lattice formalism. We perform initial calculations for a range of nuclear systems from two- to few-body neutron systems. This article is part of the theme issue 'The liminal position of Nuclear Physics: from hadrons to neutron stars'.

Shaping Electronic Flows with Strongly Correlated Physics.

Nonequilibrium quantum transport is of central importance in nanotechnology. Its description requires the understanding of strong electronic correlations that couple atomic-scale phenomena to the nanoscale. So far, research in correlated transport has focused predominantly on few-channel transport, precluding the investigation of cross-scale effects. Recent theoretical advances enable the solution of models that capture the interplay between quantum correlations and confinement beyond a few channels. This problem is the focus of this study. We consider an atomic impurity embedded in a metallic nanosheet spanning two leads, showing that transport is significantly altered by tuning only the phase of a single local hopping parameter. Furthermore─depending on this phase─correlations reshape the electronic flow throughout the sheet, either funneling it through the impurity or scattering it away from a much larger region. This demonstrates the potential for quantum correlations to bridge length scales in the design of nanoelectronic devices and sensors.

Dynamic properties and the roton mode attenuation in liquid 3He: ab initio study within the self-consistent method of moments.

The dynamic structure factor and the eigenmodes of density fluctuations in liquid 3He are studied using a novel non-perturbative approach. This new version of the self-consistent method of moments invokes up to nine sum rules and other exact relations, the two-parameter Shannon information entropy maximization procedure, and the ab initio path integral Monte Carlo simulations which provide necessary reliable input information on the system static properties. Detailed analysis is performed of the collective excitations dispersion relations, the modes' decrements and the static structure factor of 3He at the saturated vapour pressure. The results are compared to available experimental data by Albergamo et al. (Albergamo et al. 2007 Phys. Rev. Lett. 99, 205301. (doi:10.1103/PhysRevLett.99.205301)) and Fåk et al. (Fåk et al. 1994 J. Low Temp. Phys. 97, 445-487. (doi:10.1007/BF00754303)). The theory reveals a clear signature of the roton-like feature in the particle-hole segment of the excitation spectrum with a significant reduction of the roton decrement in the wavenumber range [Formula: see text]. The observed roton mode remains a well-defined collective mode even in the particle-hole band, where it is strongly damped. The existence of the roton-like mode in the bulk liquid 3He is confirmed like in other quantum fluids. The phonon branch of the spectrum is in a reasonable agreement with the same experimental data. This article is part of the theme issue 'Dynamic and transient processes in warm dense matter'.

The Solid Phase of 4He: A Monte Carlo Simulation Study.

The thermodynamics of solid (hcp) 4He is studied theoretically by means of unbiased Monte Carlo simulations at finite temperature, in a wide range of density. This study complements and extends previous theoretical work, mainly by obtaining results at significantly lower temperatures (down to 60 mK) and for systems of greater size, by including in full the effect of quantum statistics, and by comparing estimates yielded by different pair potentials. All the main thermodynamic properties of the crystal, e.g., the kinetic energy per atom, are predicted to be essentially independent of temperature below ∼ 1 K. Quantum-mechanical exchanges are virtually non-existent in this system, even at the lowest temperature considered. However, effects of quantum statistics are detectable in the momentum distribution. Comparison with available measurements shows general agreement within the experimental uncertainties.

Local Entanglement of Electrons in 1D Hydrogen Molecule.

The quantum entanglement entropy of the electrons in a one-dimensional hydrogen molecule is quantified locally using an appropriate partitioning of the two-dimensional configuration space. Both the global and the local entanglement entropy exhibit a monotonic increase when increasing the inter-nuclear distance, while the local entropy remains peaked in the middle between the nuclei with its width decreasing. Our findings show that at the inter-nuclear distance where a stable hydrogen molecule is formed, the quantum entropy shows no peculiarity thus indicating that the entropy and the energy measures display different sensitivity with respect to the interaction between the two identical electrons involved. One possible explanation is that the calculation of the quantum entropy does not account explicitly for the distance between the nuclei, which contrasts to the total energy calculation where the energy minimum depends decisively on that distance. The numerically exact and the time-dependent quantum Monte Carlo calculations show close results.

Optical properties of high-pressure fluid hydrogen across molecular dissociation.

Optical properties of compressed fluid hydrogen in the region where dissociation and metallization is observed are computed by ab initio methods and compared with recent experimental results. We confirm that at T > 3,000 K, both processes are continuous, while at T < 1,500 K, the first-order phase transition is accompanied by a discontinuity of the dc conductivity and the thermal conductivity, while both the reflectivity and absorption coefficient vary rapidly but continuously. Our results support the recent analysis of National Ignition Facility (NIF) experiments [Celliers PM, et al. (2018) Science 361:677-682], which assigned the inception of metallization to pressures where the reflectivity is ∼0.3. Our results also support the conclusion that the temperature plateau seen in laser-heated diamond-anvil cell (DAC) experiments at temperatures higher than 1,500 K corresponds to the onset of optical absorption, not to the phase transition.

Numerical Interchain Mean-Field Theory for the Specific Heat of the Bimetallic Ferromagnetically Coupled Chain Compound MnNi(NO2)4(en)2 (en = Ethylenediamine).

We present a detailed study of the field-dependent specific heat of the bimetallic ferromagnetically coupled chain compound MnNi(NO2)4(en)2, en = ethylenediamine. For this material, which in zero field orders antiferromagnetically below TN=2.45 K, small fields suppress magnetic order. Instead, in such fields, a double-peak-like structure in the temperature dependence of the specific heat is observed. We attribute this behavior to the existence of an acoustic and an optical mode in the spin-wave dispersion as a result of the existence of two different spins per unit cell. We compare our experimental data to numerical results for the specific heat obtained by exact diagonalization and Quantum Monte Carlo simulations for the alternating spin-chain model, using parameters that have been derived from the high-temperature behavior of the magnetic susceptibility. The interchain coupling is included in the numerical treatment at the mean-field level. We observe remarkable agreement between experiment and theory, including the ordering transition, using previously determined parameters. Furthermore, the observed strong effect of an applied magnetic field on the ordered state of MnNi(NO2)4(en)2 promises interesting magnetocaloric properties.

Effects of Spatial Nonlocality versus Nonlocal Causality for Bound Electrons in External Fields.

Using numerically exact solution of the time-dependent Schrödinger equation together with time-dependent quantum Monte Carlo (TDQMC) calculations, here we compare the effects of spatial nonlocality versus nonlocal causality for the ground state and for real-time evolution of two entangled electrons in parabolic potential in one spatial dimension. It was found that the spatial entanglement quantified by the linear quantum entropy is predicted with good accuracy using the spatial nonlocality, parameterized naturally within the TDQMC approach. At the same time, the nonlocal causality predicted by the exact solution leads to only small oscillations in the quantum trajectories which belong to the idler electron as the driven electron is subjected to a strong high frequency electric field, without interaction between the electrons.

Fast and accurate quantum Monte Carlo for molecular crystals.

Computer simulation plays a central role in modern-day materials science. The utility of a given computational approach depends largely on the balance it provides between accuracy and computational cost. Molecular crystals are a class of materials of great technological importance which are challenging for even the most sophisticated ab initio electronic structure theories to accurately describe. This is partly because they are held together by a balance of weak intermolecular forces but also because the primitive cells of molecular crystals are often substantially larger than those of atomic solids. Here, we demonstrate that diffusion quantum Monte Carlo (DMC) delivers subchemical accuracy for a diverse set of molecular crystals at a surprisingly moderate computational cost. As such, we anticipate that DMC can play an important role in understanding and predicting the properties of a large number of molecular crystals, including those built from relatively large molecules which are far beyond reach of other high-accuracy methods.

The Fascinating World of Low-Dimensional Quantum Spin Systems: Ab Initio Modeling.

In recent times, ab initio density functional theory has emerged as a powerful tool for making the connection between models and materials. Insulating transition metal oxides with a small spin forms a fascinating class of strongly correlated systems that exhibit spin-gap states, spin-charge separation, quantum criticality, superconductivity, etc. The coupling between spin, charge, and orbital degrees of freedom makes the chemical insights equally important to the strong correlation effects. In this review, we establish the usefulness of ab initio tools within the framework of the N-th order muffin orbital (NMTO)-downfolding technique in the identification of a spin model of insulating oxides with small spins. The applicability of the method has been demonstrated by drawing on examples from a large number of cases from the cuprate, vanadate, and nickelate families. The method was found to be efficient in terms of the characterization of underlying spin models that account for the measured magnetic data and provide predictions for future experiments.

Ca+ Ions Solvated in Helium Clusters.

We present a combined experimental and theoretical investigation on Ca+ ions in helium droplets, HeNCa+. The clusters have been formed in the laboratory by means of electron-impact ionization of Ca-doped helium nanodroplets. Energies and structures of such complexes have been computed using various approaches such as path integral Monte Carlo, diffusion Monte Carlo and basin-hopping methods. The potential energy functions employed in these calculations consist of analytical expressions following an improved Lennard-Jones formula whose parameters are fine-tuned by exploiting ab initio estimations. Ion yields of HeNCa+ -obtained via high-resolution mass spectrometry- generally decrease with N with a more pronounced drop between N=17 and N=25, the computed quantum HeNCa+ evaporation energies resembling this behavior. The analysis of the energies and structures reveals that covering Ca+ with 17 He atoms leads to a cluster with one of the smallest energies per atom. As new atoms are added, they continue to fill the first shell at the expense of reducing its stability, until N=25, which corresponds to the maximum number of atoms in that shell. Behavior of the evaporation energies and radial densities suggests liquid-like cluster structures.

Spatial Entanglement of Fermions in One-Dimensional Quantum Dots.

The time-dependent quantum Monte Carlo method for fermions is introduced and applied in the calculation of the entanglement of electrons in one-dimensional quantum dots with several spin-polarized and spin-compensated electron configurations. The rich statistics of wave functions provided by this method allow one to build reduced density matrices for each electron, and to quantify the spatial entanglement using measures such as quantum entropy by treating the electrons as identical or distinguishable particles. Our results indicate that the spatial entanglement in parallel-spin configurations is rather small, and is determined mostly by the spatial quantum nonlocality introduced by the ground state. By contrast, in the spin-compensated case, the outermost opposite-spin electrons interact like bosons, which prevails their entanglement, while the inner-shell electrons remain largely at their Hartree-Fock geometry. Our findings are in close correspondence with the numerically exact results, wherever such comparison is possible.

Confined Quantum Hard Spheres.

We present computer simulation and theoretical results for a system of N Quantum Hard Spheres (QHS) particles of diameter σ and mass m at temperature T, confined between parallel hard walls separated by a distance Hσ, within the range 1≤H≤∞. Semiclassical Monte Carlo computer simulations were performed adapted to a confined space, considering effects in terms of the density of particles ρ*=N/V, where V is the accessible volume, the inverse length H-1 and the de Broglie's thermal wavelength λB=h/2πmkT, where k and h are the Boltzmann's and Planck's constants, respectively. For the case of extreme and maximum confinement, 0.5

Reliable radical stabilization energies from diffusion Monte Carlo calculations.

We assess the performance of variational (VMC) and diffusion (DMC) quantum Monte Carlo methods for calculating the radical stabilization energies of a set of 43 carbon-centered radical species. Even using simple single-determinant trial wavefunctions, both methods perform exceptionally well, with mean absolute deviations from reference values well under the chemical accuracy standard of 1 kcal/mol. In addition, the use of DMC results in a highly concentrated spread of errors, with all 43 results within chemical accuracy at the 95% confidence level. These results indicate that DMC is an extremely reliable method for calculating radical stabilization energies and could be used as a benchmark method for larger systems in future.

Simple and Accurate Exchange Energy for Density Functional Theory.

A non-empirical exchange functional based on an interpolation between two limits of electron density, slowly varying limit and asymptotic limit, is proposed. In the slowly varying limit, we follow the study by Kleinman from 1984 which considered the response of a free-electron gas to an external periodic potential, but further assume that the perturbing potential also induces Bragg diffraction of the Fermi electrons. The interpolation function is motivated by the exact exchange functional of a hydrogen atom. Combined with our recently proposed correlation functional, tests on 56 small molecules show that, for the first-row molecules, the exchange-correlation combo predicts the total energies four times more accurately than the presently available Quantum Monte Carlo results. For the second-row molecules, errors of the core electrons exchange energies can be corrected, leading to the most accurate first- and second-row molecular total energy predictions reported to date despite minimal computational efforts. The calculated bond energies, zero point energies, and dipole moments are also presented, which do not outperform other methods.

Liquid-liquid phase transition in hydrogen by coupled electron-ion Monte Carlo simulations.

The phase diagram of high-pressure hydrogen is of great interest for fundamental research, planetary physics, and energy applications. A first-order phase transition in the fluid phase between a molecular insulating fluid and a monoatomic metallic fluid has been predicted. The existence and precise location of the transition line is relevant for planetary models. Recent experiments reported contrasting results about the location of the transition. Theoretical results based on density functional theory are also very scattered. We report highly accurate coupled electron-ion Monte Carlo calculations of this transition, finding results that lie between the two experimental predictions, close to that measured in diamond anvil cell experiments but at 25-30 GPa higher pressure. The transition along an isotherm is signaled by a discontinuity in the specific volume, a sudden dissociation of the molecules, a jump in electrical conductivity, and loss of electron localization.

Nuclear quantum effects induce metallization of dense solid molecular hydrogen.

We present an accurate computational study of the electronic structure and lattice dynamics of solid molecular hydrogen at high pressure. The band-gap energies of the C2/c, Pc, and P63/m structures at pressures of 250, 300, and 350 GPa are calculated using the diffusion quantum Monte Carlo (DMC) method. The atomic configurations are obtained from ab initio path-integral molecular dynamics (PIMD) simulations at 300 K and 300 GPa to investigate the impact of zero-point energy and temperature-induced motion of the protons including anharmonic effects. We find that finite temperature and nuclear quantum effects reduce the band-gaps substantially, leading to metallization of the C2/c and Pc phases via band overlap; the effect on the band-gap of the P63/m structure is less pronounced. Our combined DMC-PIMD simulations predict that there are no excitonic or quasiparticle energy gaps for the C2/c and Pc phases at 300 GPa and 300 K. Our results also indicate a strong correlation between the band-gap energy and vibron modes. This strong coupling induces a band-gap reduction of more than 2.46 eV in high-pressure solid molecular hydrogen. Comparing our DMC-PIMD with experimental results available, we conclude that none of the structures proposed is a good candidate for phases III and IV of solid hydrogen. © 2017 Wiley Periodicals, Inc.

Quantum monte carlo study of the energetics of small hydrogenated and fluoride lithium clusters.

An investigation of the energetics of small lithium clusters doped either with a hydrogen or with a fluorine atom as a function of the number of lithium atoms using fixed-node diffusion quantum Monte Carlo (DMC) simulation is reported. It is found that the binding energy (BE) for the doped clusters increases in absolute values leading to a more stable system than for the pure ones in excellent agreement with available experimental measurements. The BE increases for pure, remains almost constant for hydrogenated, and decreases rapidly toward the bulk lithium for the fluoride as a function of the number of lithium atoms in the clusters. The BE, dissociation energy as well as the second difference in energy display a pronounced odd-even oscillation with the number of lithium atoms. The electron correlation inverts the odd-even oscillation pattern for the doped in comparison with the pure clusters and has an impact of 29%-83% to the BE being higher in the pure cluster followed by the hydrogenated and then by the fluoride. The dissociation energy and the second difference in energy indicate that the doped cluster Li3 H is the most stable whereas among the pure ones the more stable are Li2 , Li4 , and Li6 . The electron correlation energy is crucial for the stabilization of Li3 H. © 2016 Wiley Periodicals, Inc.

Quantum Monte Carlo with very large multideterminant wavefunctions.

An algorithm to compute efficiently the first two derivatives of (very) large multideterminant wavefunctions for quantum Monte Carlo calculations is presented. The calculation of determinants and their derivatives is performed using the Sherman-Morrison formula for updating the inverse Slater matrix. An improved implementation based on the reduction of the number of column substitutions and on a very efficient implementation of the calculation of the scalar products involved is presented. It is emphasized that multideterminant expansions contain in general a large number of identical spin-specific determinants: for typical configuration interaction-type wavefunctions the number of unique spin-specific determinants Ndetσ ( σ=↑,↓) with a non-negligible weight in the expansion is of order O(Ndet). We show that a careful implementation of the calculation of the Ndet -dependent contributions can make this step negligible enough so that in practice the algorithm scales as the total number of unique spin-specific determinants,  Ndet↑+Ndet↓, over a wide range of total number of determinants (here, Ndet up to about one million), thus greatly reducing the total computational cost. Finally, a new truncation scheme for the multideterminant expansion is proposed so that larger expansions can be considered without increasing the computational time. The algorithm is illustrated with all-electron fixed-node diffusion Monte Carlo calculations of the total energy of the chlorine atom. Calculations using a trial wavefunction including about 750,000 determinants with a computational increase of ∼400 compared to a single-determinant calculation are shown to be feasible. © 2016 Wiley Periodicals, Inc.