Path Integral Monte Carlo Simulations Research Articles

Diamagnetic susceptibility from a nonadiabatic path-integral simulation of few-electron systems

Diamagnetism is the response of dynamical compositions of charged particles, electrons, and nuclei, to an incident magnetic field. In this paper, we study how the finite temperature and finite nuclear masses affect the diamagnetic susceptibilities of selected small atoms and molecules, as limiting cases of dilute gas. We use nonrelativistic path-integral Monte Carlo simulation (PIMC), where both electrons and nuclei are treated on equal footing at finite temperatures in sampling exact Coulomb pair density matrices. The PIMC estimator of diamagnetic susceptibility has been briefly introduced in Ceperley [D. M. Ceperley, Rev. Mod. Phys. 67, 279 (1995)], but here we present a comprehensive derivation, discussion of practical effects, and proof-of-concept results for selected few-body Coulomb systems. Our results are in perfect agreement with high-accuracy literature references, where available, but also demonstrate additional thermal effects of the diamagnetic response of low-mass systems.

Meta-GGA exchange-correlation free energy density functional to increase the accuracy of warm dense matter simulations

We discuss strategies for thermalization of the ground-state meta-generalized gradient approximation (meta-GGA) exchange-correlation (XC) functionals. A simple but accurate scheme is implemented via universal additive thermal correction to XC using a perturbativelike self-consistent approach. The additive correction with explicit temperature dependence is applied to the ground-state deorbitalized, strongly constrained, and appropriately normed (SCAN-L) meta-GGA XC leading to a thermal XC functional denoted here as T-SCAN-L. The thermal T-SCAN-L meta-GGA functional shows significant improvement in density functional theory calculation accuracy for warm dense matter by a factor of 3 to 10, achieving an accuracy of total pressure between a few tenths and $\ensuremath{\sim}1$% when compared to traditional XC functionals, as demonstrated by the comparison to path-integral Monte Carlo simulations for helium equation of state. The T-SCAN-L calculations of dc conductivity of warm dense aluminum also give better agreement with experiments over other XC functionals such as PBE and SCAN-L.

Nonlinear interaction of external perturbations in warm dense matter

AbstractWe present extensive new ab initio path integral Monte Carlo (PIMC) results for an electron gas at warm dense matter conditions that is subject to multiple harmonic perturbations. In addition to the previously investigated nonlinear effects at the original wave number (Dornheim et al., Phys. Rev. Lett., 2020, 125, 085001) and the excitation of higher harmonics (Dornheim et al., Phys. Rev. Res., 2021, 3, 033231), the presence of multiple external potentials leads to mode‐coupling effects, which constitute the dominant nonlinear effect and lead to a substantially more complicated density response compared to linear response theory. One possibility to estimate mode‐coupling effects from a PIMC simulation of the unperturbed system is given in terms of generalized imaginary‐time correlation functions that have been recently introduced by Dornheim et al. (J. Chem. Phys., 2021, 155, 054110). In addition, we extend our previous analytical theory of the nonlinear density response of the electron gas in terms of the static local field correction (Dornheim et al., 2020, Phys. Rev. Lett., 125, 235001), which allows for a highly accurate description of the PIMC results with negligible computational cost.

Bound States of the Exchange—Correlation Excitons in the Uniform Electron Gas by the Monte Carlo Simulations

The modified path integral representation of Wigner functions and the new Monte Carlo approach has been suggested to account for the impact of the interparticle interaction on the Pauli exclusion principle of fermions. This approach also allows to calculate the momentum distribution functions and to reduce the “sign problem” that is inaccessible to the standard path integral Monte Carlo methods. The obtained pair electron–electron distribution functions for the “uniform electron gas” demonstrate the short-range quantum ordering of electrons associated with exchange-correlation excitons. The exchange-correlation exciton is caused by the interaction of electrons with positively charged exchange holes and the excluded volume effect. The developed approach allows one to study the density–temperature range of the exciton arising, existence, and decay. Using the potential of the mean force and semiclassical Bohr–Sommerfeld quantization condition, we have demonstrated the existence of bound states disturbing the Maxwellian distribution and estimated their average energy levels. The exchange-correlation excitons have not been observed earlier in the standard path integral Monte Carlo simulations.

Path integral Monte Carlo approach to the structural properties and collective excitations of liquid ^3{text {He}} without fixed nodes

Due to its nature as a strongly correlated quantum liquid, ultracold helium is characterized by the nontrivial interplay of different physical effects. Bosonic ^4{text {He}} exhibits superfluidity and Bose-Einstein condensation. Its physical properties have been accurately determined on the basis of ab initio path integral Monte Carlo (PIMC) simulations. In contrast, the corresponding theoretical description of fermionic ^3{text {He}} is severely hampered by the notorious fermion sign problem, and previous PIMC results have been derived by introducing the uncontrolled fixed-node approximation. In this work, we present extensive new PIMC simulations of normal liquid ^3{text {He}} without any nodal constraints. This allows us to to unambiguously quantify the impact of Fermi statistics and to study the effects of temperature on different physical properties like the static structure factor S({mathbf {q}}), the momentum distribution n({mathbf {q}}), and the static density response function chi ({mathbf {q}}). In addition, the dynamic structure factor S({mathbf {q}},omega ) is rigorously reconstructed from imaginary-time PIMC data. From simulations of ^3{text {He}}, we derived the familiar phonon–maxon–roton dispersion function that is well-known for ^4{text {He}} and has been reported previously for two-dimensional ^3{text {He}} films (Nature 483:576–579 (2012)). The comparison of our new results for both S({mathbf {q}}) and S({mathbf {q}},omega ) with neutron scattering measurements reveals an excellent agreement between theory and experiment.

Finite-temperature phases of trapped bosons in a two-dimensional quasiperiodic potential

We study a system of 2D trapped bosons in a quasiperiodic potential via ab initio Path Integral Monte Carlo simulations, focusing on its finite temperature properties, which have not yet been explored. Alongside the superfluid, normal fluid and insulating phases, we demonstrate the existence of a Bose glass phase, which is found to be robust to thermal fluctuations, up to about half of the critical temperature of the non-interacting system. Local quantities in the trap are characterized by employing zonal estimators, allowing us to trace a phase diagram; we do so for a set of parameters within reach of current experiments with quasi-2D optical confinement.

Path integral Monte Carlo simulations of the geometrical effects in KDP crystals

Path integral Monte Carlo (PIMC) simulations with very simple models were used in order to unveil the physics behind the isotope effects in H-bonded ferroelectrics. First, we studied geometrical effects in the H-bonds caused by deuteration with a general three-site model based on a back-to-back double Morse potential plus a Morse potential between oxygens, fitted to explain different general features for a wide set of H-bonded compounds. Our model results show the Ubbelohde or geometrical effect (GE), i.e., the expansion of the H-bond with deuteration, in agreement to what is observed in H-bonded ferroelectrics with short H-bonds. Moreover, adjusting the potential parameters to ab initio results, we have developed a 1D model which considers the bilinear proton-proton interaction in mean-field to study nuclear quantum effects that give rise to the GE in KDP crystals. PIMC simulations reveal that protons tunnel more efficiently than deuterons along the 1D chain, giving rise to a strong attraction center that pulls the oxygens together. This mechanism, which is based on the correlation between tunneling and geometrial modifications of the H-bonds, leads to a strong GE in the ordered phase of the chain at low temperature which is in good agreement with the experimental data.

Monte Carlo simulations of the electron short-range quantum ordering in Coulomb systems and the ‘fermionic sign problem’

To account for the interference effects of the Coulomb and exchange interactions of electrons the new path integral representation of the density matrix has been developed in the canonical ensemble at finite temperatures. The developed representation allows to reduce the notorious ‘fermionic sign problem’ in the path integral Monte Carlo simulations of fermionic systems. The obtained results for pair distribution functions in plasma and uniform electron gas demonstrate the short-range quantum ordering of electrons associated in literature with exchange-correlation excitons. The charge estimations show the excitonic electric neutrality. Comparison of the internal energy with available ones in the literature demonstrates that the short range ordering does not give noticeable contributions to integral thermodynamic characteristics. This fine physical effect was not observed earlier in the standard path integral Monte Carlo simulations.

Ab initio thermodynamics of one-component plasma for astrophysics of white dwarfs and neutron stars

ABSTRACT Using path-integral Monte Carlo (PIMC) simulations, we have calculated energy of a crystal composed of atomic nuclei and uniform incompressible electron background in the temperature and density range, covering fully ionized layers of compact stellar objects, white dwarfs, and neutron stars, including the high-density regime, where ion quantization is important. We have approximated the results by convenient analytic formulae, which allowed us to integrate and differentiate the energy with respect to temperature and density to obtain various thermodynamic functions such as Helmholtz free energy, specific heat, pressure, entropy etc. In particular, we have demonstrated, that the total crystal specific heat can exceed the well-known harmonic lattice contribution by a factor of 1.5 due to anharmonic effects. By combining our results with the PIMC thermodynamics of a quantum Coulomb liquid, updated in the present work, we were able to determine density dependences of such melting parameters as the Coulomb coupling strength at melting, latent heat, and a specific heat jump. Our results are necessary for realistic modelling of thermal evolution of compact degenerate stars.

Single-momentum path integral Monte Carlo simulations of uniform electron gas in warm dense matter regime

In this paper, the single-momentum path integral Monte Carlo method, previously developed for simple quantum systems and hydrogen plasma, is adapted to simulations of the uniform electron gas. The developed method is based on the combination of Wigner formalism and the path integral approach and is able to calculate various thermodynamic values and distribution functions without differentiation of the partition function. Since the exchange interaction between electrons is taken into account by the Gram determinants of the exchange matrix, the fermionic sign problem is reduced significantly, and in the case of coordinate-depending variables, is completely eliminated. The method was applied to study thermodynamic properties of the uniform electron gas in warm dense matter regime. Average kinetic, potential, and exchange-correlation energy were calculated in a wide range of states.

Momentum distribution of the uniform electron gas at finite temperature: Effects of spin polarization.

We carry out extensive direct path integral Monte Carlo (PIMC) simulations of the uniform electron gas (UEG) at finite temperature for different values of the spin-polarization ξ. This allows us to unambiguously quantify the impact of spin effects on the momentum distribution function n(k) and related properties. We find that interesting physical effects like the interaction-induced increase in the occupation of the zero-momentum state n(0) substantially depend on ξ. Our results further advance the current understanding of the UEG as a fundamental model system, and are of practical relevance for the description of transport properties of warm dense matter in an external magnetic field. All PIMC results are freely available online and can be used as a benchmark for the development of methods and applications.

Quasiparticle Nature of the Bose Polaron at Finite Temperature.

The Bose polaron has attracted theoretical and experimental interest because the mobile impurity is surrounded by a bath that undergoes a superfluid-to-normal phase transition. Although many theoretical works have studied this system in its ground state, only a few analyze its behavior at finite temperature. We have studied the effect of temperature on a Bose polaron system performing abinitio path integral MonteCarlo simulations. This method is able to approach the critical temperature without losing accuracy, in contrast with perturbative approximations. We have calculated the polaron energy for the repulsive and attractive branches and we have observed an asymmetric behavior between the two branches. When the potential is repulsive, the polaron energy decreases when the temperature increases, and contrariwise for the attractive branch. Our results for the effective mass and the dynamical structure factor of the polaron show unambiguously that its quasiparticle nature disappears close to the critical temperature, in agreement with recent experimental findings. Finally, we have also estimated the fraction of bosons in the condensate as well as the superfluid fraction, and we have concluded that the impurity hinders the condensation of the rest of bosons.

Finite-temperature critical behavior of long-range quantum Ising models

We study the phase diagram and critical properties of quantum Ising chains with long-range ferromagnetic interactions decaying in a power-law fashion with exponent \alphaα, in regimes of direct interest for current trapped ion experiments. Using large-scale path integral Monte Carlo simulations, we investigate both the ground-state and the nonzero-temperature regimes. We identify the phase boundary of the ferromagnetic phase and obtain accurate estimates for the ferromagnetic-paramagnetic transition temperatures. We further determine the critical exponents of the respective transitions. Our results are in agreement with existing predictions for interaction exponents \alpha<1α>1 up to small deviations in some critical exponents. We also address the elusive regime \alpha < 1α<1, where we find that the universality class of both the ground-state and nonzero-temperature transition is consistent with the mean-field limit at \alpha = 0α=0. Our work not only contributes to the understanding of the equilibrium properties of long-range interacting quantum Ising models, but can also be important for addressing fundamental dynamical aspects, such as issues concerning the open question of thermalization in such models.

Virial expansion of the electrical conductivity of hydrogen plasmas.

The low-density limit of the electrical conductivity σ(n,T) of hydrogen as the simplest ionic plasma is presented as a function of the temperature T and mass density n in the form of a virial expansion of the resistivity. Quantum statistical methods yield exact values for the lowest virial coefficients which serve as a benchmark for analytical approaches to the electrical conductivity as well as for numerical results obtained from density functional theory-based molecular dynamics simulations (DFT-MD) or path-integral Monte Carlo simulations. While these simulations are well suited to calculate σ(n,T) in a wide range of density and temperature, in particular, for the warm dense matter region, they become computationally expensive in the low-density limit, and virial expansions can be utilized to balance this drawback. We present new results of DFT-MD simulations in that regime and discuss the account of electron-electron collisions by comparison with the virial expansion.

Integral equation theory based dielectric scheme for strongly coupled electron liquids.

In a recent paper, Lucco Castello et al. (arXiv:2107.03537) provided an accurate parameterization of classical one-component plasma bridge functions that was embedded in a novel dielectric scheme for strongly coupled electron liquids. Here, this approach is rigorously formulated, its set of equations is formally derived, and its numerical algorithm is scrutinized. A systematic comparison with available and new path integral Monte Carlo simulations reveals a rather unprecedented agreement especially in terms of the interaction energy and the long wavelength limit of the static local field correction.

Thermodynamics of the uniform electron gas: Fermionic path integral Monte Carlo simulations in the restricted grand canonical ensemble

The uniform electron gas (UEG) is one of the key models for the understanding of warm dense matter—an exotic, highly compressed state of matter between solid and plasma phases. The difficulty in modelling the UEG arises from the need to simultaneously account for Coulomb correlations, quantum effects, and exchange effects, as well as finite temperature. The most accurate results so far were obtained from quantum Monte Carlo (QMC) simulations with a variety of representations. However, QMC for electrons is hampered by the fermion sign problem. Here, we present results from a novel fermionic propagator path integral Monte Carlo in the restricted grand canonical ensemble. The ab initio simulation results for the spin‐resolved pair distribution functions and static structure factor are reported for two isotherms (T in the units of the Fermi temperature). Furthermore, we combine the results from the linear response theory in the Singwi‐Tosi‐Land‐Sjölander scheme with the QMC data to remove finite‐size errors in the interaction energy. We present a new corrected parametrization for the interaction energy and the exchange–correlation free energy in the thermodynamic limit, and benchmark our results against the restricted path integral Monte Carlo by Brown et al. [Phys. Rev. Lett. 110, 146405 (2013)] and configuration path integral Monte Carlo/permutation‐blocking path integral Monte Carlo by Dornheim et al. [Phys. Rev. Lett. 117, 115701 (2016)].

Density response of the warm dense electron gas beyond linear response theory: Excitation of harmonics

In a recent Letter, Dornheim et al. [PRL 125, 085001 (2020)] have investigated the nonlinear density response of the uniform electron gas in the warm dense matter regime. More specifically, they have studied the cubic response function at the first harmonic, which cannot be neglected in many situations of experimental relevance. In this work, we go one step further and study the full spectrum of excitations at the higher harmonics of the original perturbation based on extensive new ab initio path integral Monte Carlo (PIMC) simulations. We find that the dominant contribution to the density response beyond linear response theory is given by the quadratic response function at the second harmonic in the moderately nonlinear regime. Furthermore, we show that the nonlinear density response is highly sensitive to exchange-correlation effects, which makes it a potentially valuable new tool of diagnostics. To this end, we present a new theoretical description of the nonlinear electronic density response based on the recent effective static approximation to the local field correction [PRL 125, 235001 (2020)], which accurately reproduces our PIMC data with negligible computational cost.

Nonlinear electronic density response of the ferromagnetic uniform electron gas at warm dense matter conditions

AbstractIn a recent Letter [T. Dornheim et al., Phys. Rev. Lett. 125, 085001 (2020)], we have presented the first ab initio results for the nonlinear density response of electrons in the warm dense matter (WDM) regime. In the present work, we extend these efforts by carrying out extensive new path integral Monte Carlo simulations of a ferromagnetic electron gas that is subject to an external harmonic perturbation. This allows us to unambiguously quantify the impact of spin‐effects on the nonlinear density response of the warm dense electron gas. In addition to their utility for the description of WDM in an external magnetic field, our results further advance our current understanding of the uniform electron gas as a fundamental model system, which is important in its own right.

Fermion sign problem in path integral Monte Carlo simulations: grand-canonical ensemble

We present a practical analysis of the fermion sign problem in fermionic path integral Monte Carlo (PIMC) simulations in the grand-canonical ensemble (GCE). As a representative model system, we consider electrons in a 2D harmonic trap. We find that the sign problem in the GCE is even more severe than in the canonical ensemble at the same conditions, which, in general, makes the latter the preferred option. Despite these difficulties, we show that fermionic PIMC simulations in the GCE are still feasible in many cases, which potentially gives access to important quantities like the compressibility or the Matsubara Greens function. This has important implications for contemporary fields of research such as warm dense matter, ultracold atoms, and electrons in quantum dots.

Momentum distribution function and short-range correlations of the warm dense electron gas: Ab initio quantum Monte Carlo results.

In a classical plasma the momentum distribution, n(k), decays exponentially, for large k, and the same is observed for an ideal Fermi gas. However, when quantum and correlation effects are relevant simultaneously, an algebraic decay, n_{∞}(k)∼k^{-8} has been predicted. This is of relevance for cross sections and threshold processes in dense plasmas that depend on the number of energetic particles. Here we present extensive ab initio results for the momentum distribution of the nonideal uniform electron gas at warm dense matter conditions. Our results are based on first principle fermionic path integral Monte Carlo (CPIMC) simulations and clearly confirm the k^{-8} asymptotic. This asymptotic behavior is directly linked to short-range correlations which are analyzed via the on-top pair distribution function (on-top PDF), i.e., the PDF of electrons with opposite spin. We present extensive results for the density and temperature dependence of the on-top PDF and for the momentum distribution in the entire momentum range.