Quantum Monte Carlo Study Research Articles

Molecular to atomic phase transition in hydrogen under high pressure.

The metallization of high-pressure hydrogen, together with the associated molecular to atomic transition, is one of the most important problems in the field of high-pressure physics. It is also currently a matter of intense debate due to the existence of conflicting experimental reports on the observation of metallic hydrogen on a diamond-anvil cell. Theoretical calculations have typically relied on a mean-field description of electronic correlation through density functional theory, a theory with well-known limitations in the description of metal-insulator transitions. In fact, the predictions of the pressure-driven dissociation of molecules in high-pressure hydrogen by density functional theory is strongly affected by the chosen exchange-correlation functional. In this Letter, we use quantum MonteCarlo calculations to study the molecular to atomic transition in hydrogen. We obtain a transition pressure of 447(3)GPa, in excellent agreement with the best experimental estimate of the transition 450 GPa based on an extrapolation to zero band gap from experimental measurements. Additionally, we find that C2/c is stable almost up to the molecular to atomic transition, in contrast to previous density functional theory (DFT) and DFT+quantum MonteCarlo studies which predict large stability regimes for intermediary molecular phases.

Anomalous quantum glass of bosons in a random potential in two dimensions.

We present a quantum MonteCarlo study of the "quantum glass" phase of the two-dimensional Bose-Hubbard model with random potentials at filling ρ=1. In the narrow region between the Mott and superfluid phases, the compressibility has the form κ∼exp(-b/T^{α})+c with α<1 and c vanishing or very small. Thus, at T=0 the system is either incompressible (a Mott glass) or nearly incompressible (a Mott-glass-like anomalous Bose glass). At stronger disorder, where a glass reappears from the superfluid, we find a conventional highly compressible Bose glass. On a path connecting these states, away from the superfluid at larger Hubbard repulsion, a change of the disorder strength by only 10% changes the low-temperature compressibility by more than 4 orders of magnitude, lending support to two types of glass states separated by a phase transition or a sharp crossover.

A quantum Monte Carlo study of confined quantum systems: application to harmonic oscillator and hydrogenic-like atoms

The correlation function quantum Monte Carlo (CFQMC) approach is employed to study the energy spectra of confined quantum systems. This method, applied originally to determine rovibrational eigenenergies of molecules, is utilized here to calculate the energy levels of hydrogen atom, helium cation, lithium dication and two confined harmonic oscillator (HO) models: the one-dimensional HO within a box of impenetrable walls and the three-dimensional one confined by an impenetrable spherical box. The dependence of the eigenenergies on functional form and the number of the basis functions are analyzed for various confinement parameters. The present results are compared with those previously published, and the efficiency of the CFQMC method to treat confined quantum systems is discussed.

An auxiliary-field quantum Monte Carlo study of the chromium dimer.

The chromium dimer (Cr2) presents an outstanding challenge for many-body electronic structure methods. Its complicated nature of binding, with a formal sextuple bond and an unusual potential energy curve (PEC), is emblematic of the competing tendencies and delicate balance found in many strongly correlated materials. We present an accurate calculation of the PEC and ground state properties of Cr2, using the auxiliary-field quantum Monte Carlo (AFQMC) method. Unconstrained, exact AFQMC calculations are first carried out for a medium-sized but realistic basis set. Elimination of the remaining finite-basis errors and extrapolation to the complete basis set limit are then achieved with a combination of phaseless and exact AFQMC calculations. Final results for the PEC and spectroscopic constants are in excellent agreement with experiment.

Pair correlation functions of FeAs-based superconductors: Quantum Monte Carlo study

The new generalized quantum continuous time world line Monte Carlo algorithm was developed to calculate pair correlation functions for two-dimensional FeAs-clusters modeling of iron-based superconductors within the framework of the two-orbital model. The analysis of pair correlations depending on the cluster size, temperature, interaction, and the type of symmetry of the order parameter is carried out. The data obtained for clusters with sizes up to 1 0x1 0 FeAs-cells favor the possibility of an effective charge carrier's attraction that is corresponding the A1g-symmetry, at some parameters of interaction.

A quantum Monte Carlo study on electron correlation effects in small aluminum hydride clusters

Using accurate methods we calculate binding energies to discuss the electron–electron interaction in the formation of AlnHm ionic clusters.

Conformal field theories at nonzero temperature: Operator product expansions, Monte Carlo, and holography

We compute the non-zero temperature conductivity of conserved flavor currents in conformal field theories (CFTs) in 2+1 spacetime dimensions. At frequencies much greater than the temperature, $\hbar\omega>> k_B T$, the $\omega$ dependence can be computed from the operator product expansion (OPE) between the currents and operators which acquire a non-zero expectation value at T > 0. Such results are found to be in excellent agreement with quantum Monte Carlo studies of the O(2) Wilson-Fisher CFT. Results for the conductivity and other observables are also obtained in vector 1/N expansions. We match these large $\omega$ results to the corresponding correlators of holographic representations of the CFT: the holographic approach then allows us to extrapolate to small $\hbar \omega/(k_B T)$. Other holographic studies implicitly only used the OPE between the currents and the energy-momentum tensor, and this yields the correct leading large $\omega$ behavior for a large class of CFTs. However, for the Wilson-Fisher CFT a relevant "thermal" operator must also be considered, and then consistency with the Monte Carlo results is obtained without a previously needed ad hoc rescaling of the T value. We also establish sum rules obeyed by the conductivity of a wide class of CFTs.

The effect of FM inter-ladder coupling in spin-1/2 AFM two-leg ladders in the presence of a magnetic field: Quantum Monte Carlo study

We study the effect of inter-ladder ferromagnetic (FM) coupling in spin-1/2 two-leg ladders with antiferromagnetic (AFM) legs and rungs interactions using the stochastic series expansion quantum Monte Carlo. We have compared the results with the experimental measurement on Sr14−xCaxCu24O41 cuprate which is the candidate for spin-1/2 AFM two-leg ladders with FM inter-ladder interaction. A remarkable asymptotic behavior of susceptibility is observed at very low temperature. In the absence of the magnetic field, thermodynamic behavior of an individual spin-1/2 two-leg ladder is similar to coupled one up to −0.5Jleg interaction. But, the gaped phase is not clear in the Jin=−0.2Jleg of FM coupled two-leg ladder even at low magnetic fields, which shows that the inter-ladder FM interaction can induce a new quantum ordered gapless phase at zero temperature.

Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods.

Highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. The results demonstrate that the lithium-carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.

Electrically controllable magnetic order in the bilayer Hubbard model on honeycomb lattice: A determinant quantum Monte Carlo study

In this paper, we use the determinant quantum Monte Carlo method to study the effect of the electric field on the magnetic order in a bilayer Hubbard model on a honeycomb lattice, in which only the direct interlayer hopping energy is included. Our results qualitatively support the layered antiferromagnetic, spin-density wave ground state found in the mean-field theory at the charge neutrality point. The obtained magnetic moments, however, are much smaller than what are estimated in the mean-field theory. As the electric field increases, the magnetic order parameter rapidly decreases.

Quantum Monte Carlo study of one-dimensional transition-metal organometallic cluster systems and their suitability as spin filters

We present calculations of electronic and magnetic structures of vanadium-benzene multidecker clusters V$_{n}$Bz$_{n+1}$ ($n$ = 1 - 3) using advanced quantum Monte Carlo methods. These and related systems have been identified as prospective spin filters in spintronic applications, assuming that their ground states are half-metallic ferromagnets. Although we find that magnetic properties of these multideckers are consistent with ferromagnetic coupling, their electronic structures do not appear to be half-metallic as previously assumed. In fact, they are ferromagnetic insulators with large and broadly similar $\uparrow$-/$\downarrow$-spin gaps. This makes the potential of these and related materials as spin filtering devices very limited, unless they are further modified or functionalized.

From hypernuclei to the Inner Core of Neutron Stars: A Quantum Monte Carlo Study

Auxiliary Field Diffusion Monte Carlo (AFDMC) calculations have been employed to revise the interaction beween A-hyperons and nucleons in hypernuclei. The scheme used to describe the interaction, inspired by the phenomenological Argonne-Urbana forces, is the ΛN + ΛNN potential firstly introduced by Bodmer, Usmani et al. Within this framework, we performed calculations on light and medium mass hypernuclei in order to assess the extent of the repulsive contribution of the three-body part. By tuning this contribution in order to reproduce the Λ separation energy in 5ΛHe and 17ΛO, experimental findings are reproduced over a wide range of masses. Calculations have then been extended to Λ-neutron matter in order to derive an analogous of the symmetry energy to be used in determining the equation of state of matter in the typical conditions found in the inner core of neutron stars.

Quantum Monte Carlo study of strongly interacting Fermi gases

In recent years Quantum Monte Carlo techniques provided to be a valuable tool to study strongly interacting Fermi gases at zero temperature. We have used QMC methods to investigate several properties of the two-components Fermi gas at unitarity and in the BCS-BEC crossover, both with equal and unequal masses corresponding to the Li – K Fermi mixture. In this paper we present several recent QMC results, including the energy at zero and finite effective range, the contact parameter and the static structure factor, which, at low momentum, depends strongly on the phonons in the unitary Fermi gas.

Pair correlations in iron-based superconductors: Quantum Monte Carlo study

Abstract The new generalized quantum continuous time world line Monte Carlo algorithm was developed to calculate pair correlation functions for two-dimensional FeAs-clusters modeling of iron-based superconductors using a two-orbital model. The data obtained for clusters with sizes up to 10 × 10 FeAs-cells favor the possibility of an effective charge carrier's attraction that is corresponding the A 1 g -symmetry, at some parameters of interaction. The analysis of pair correlations depending on the cluster size, temperature, interaction, and the type of symmetry of the order parameter is carried out.

A quantum Monte Carlo study of zinc-porphyrin: Vertical excitation between the singlet ground state and the lowest-lying singlet excited state

We have calculated the vertical excitation energy between the singlet ground state (11Ag) and the lowest-lying singlet excited state (11Eu) of Zn-porphyrin employing the fixed-node diffusion Monte Carlo technique. The determinantal parts of trial wave functions were constructed using results from Configuration Interaction and time-dependent Density Functional Theory.

Energy density matrix formalism for interacting quantum systems: Quantum Monte Carlo study

We develop an energy density matrix that parallels the one-body reduced density matrix (1RDM) for many-body quantum systems. Just as the density matrix gives access to the number density and occupation numbers, the energy density matrix yields the energy density and orbital occupation energies. The eigenvectors of the matrix provide a natural orbital partitioning of the energy density while the eigenvalues comprise a single-particle energy spectrum obeying a total energy sum rule. For mean-field systems the energy density matrix recovers the exact spectrum. When correlation becomes important, the occupation energies resemble quasiparticle energies in some respects. We explore the occupation energy spectrum for the finite 3D homogeneous electron gas in the metallic regime and an isolated oxygen atom with ground-state quantum Monte Carlo techniques implemented in the qmcpack simulation code. The occupation energy spectrum for the homogeneous electron gas can be described by an effective mass below the Fermi level. Above the Fermi level evanescent behavior in the occupation energies is observed in similar fashion to the occupation numbers of the 1RDM. A direct comparison with total energy differences shows a quantitative connection between the occupation energies and electron addition and removal energies for the electron gas. For the oxygen atom, the association between the ground-state occupation energies and particle addition and removal energies becomes only qualitative. The energy density matrix provides an avenue for describing energetics with quantum Monte Carlo methods which have traditionally been limited to total energies.

Magnetic and pairing properties of a two-orbital model for the pnictide superconductors: a quantum Monte Carlo study

Using the constrained-path Monte Carlo method, a two-orbital model for the pnictide superconductors is studied at half filling and in both the electron- and hole-doped cases. At half filling, a stable (π, 0)/(0, π) magnetic order is explicitly observed and the system tends to be in an orthomagnetic order rather than the striped antiferromagnetic order on increasing the Coulomb repulsion U. In the electron-doped case, the (π, 0)/(0, π) magnetic order is enhanced upon doping and suppressed eventually and a s± pairing state dominates all the possible nearest-neighbour-bond pairings. Whereas in the hole-doped case, the magnetic order is straightforwardly suppressed and two nearly degenerate A1g and B1g intraband pairings become the dominant ones.

Quantum Monte Carlo Study of the Protonated Water Dimer.

We report an extensive theoretical study of the protonated water dimer H5O2(+) (Zundel ion) by means of the highly correlated variational Monte Carlo and lattice regularized Monte Carlo approaches. This system represents the simplest model for proton transfer (PT), and a correct description of its properties is essential in order to understand the PT mechanism in more complex aqueous systems. Our Jastrow correlated AGP wave function ensures an accurate treatment of electron correlation. By exploiting the advantage of contracting the primitive basis set over atomic hybrid orbitals, we are able to limit dramatically the number of variational parameters with a systematic control on the numerical precision, a crucial ingredient in order to simulate larger systems. For both energetics and geometrical properties, our QMC results are found to be in excellent agreement with state-of-the-art coupled cluster CCSD(T) techniques. A comparison with density functional theory in the PBE approximation points to the crucial role of electron correlation for a correct description of the PT in the dimer. We prove that the QMC framework used in this work is able to resolve the tiny energy differences (∼0.3 kcal/mol) and structural variations involved in proton transfer reactions. Our approach combines these features and a favorable N(4) scaling with the number of particles which paves the way to the simulation of more realistic PT models. A test calculation on a larger protonated water cluster is carried out. The QMC approach used here represents a promising candidate to provide the first high-level ab initio description of PT in water.

Quantum Monte Carlo for activated reactions at solid surfaces: Time well spent on stretched bonds

Many chemical reactions involve bond‐dissociation. This is also true for reactions at solid surfaces, in which the dissociation step is often limiting but facilitated in comparison to gas‐phase reaction channels. This work considers N2 dissociation. The molecule is strongly bound and stretched geometries are chosen. Heterogeneous catalysis by copper is simulated. It was investigated in our previous work as it is in many ways a prototype metal presenting a close‐packed surface here. These nitrogen molecules are adsorbed on copper and fixed geometries on the dissociation reaction pathway for stretched N2 are given using density functional theory (DFT) calculations in a plane‐wave basis. This dissociating molecule appears to be underbound using the ab initio Perdew, Burke, Ernzerhof (PBE) DFT functional but while this phenomenon accounts for a few percent at 5 Å, at 6 Å, PBE gives less than 30% of the binding energy. This indicates the onset of dissociation. The PBE wave‐functions at these bond‐lengths serve as trial input for Quantum Monte Carlo (QMC) simulations of the ground states to obtain highly accurate correlated results for the associated activation barriers indicating the catalytic effect on this dissociation. The geometries from this bond‐stretching study mimic the transition state (TS). This procedure requires no search for the actual TS geometry. Finite‐size effects and fixed‐node error are possible limitations to accuracy of this type of QMC study. We are able to limit fixed‐node error, using certain trial wave‐functions. The finite‐size effect is considerable, although comparing two adsorbed geometries cancels about 90% with respect to clean surfaces. Unfolding the cell to simulate a 9 k‐point grid (rather than a single k‐point) reduces the remainder by at least a factor 130 but relations for calibrating the remaining (2 mHa) error on converged grids are also used. The pseudopotential used to represent the atomic core of copper must also be determined carefully: we leave 11 active electrons but include the 3d shell in the pseudopotential. © 2014 Wiley Periodicals, Inc.

Two-species hard-core bosons on the triangular lattice: A quantum Monte Carlo study

Using worm-type quantum Monte Carlo simulations, we investigate bosonic mixtures on the triangular lattice of two species of bosons, which interact via nearest-neighbour intraspecies ($V$) and onsite interspecies ($U$) repulsions. For the case of symmetric hopping amplitude ($t_A/V=t_B/V$) and $U/V=1$, we determine a rich ground-state phase diagram that contains double solid, double superfluid (2SF), supersolid (SS), solid-superfluid (Solid-SF) and counterflow supersolid (CSS) states. The SS, Solid-SF and CSS states exhibit spontaneous symmetry breaking among the three sublattices of the triangular lattice and between the two species, which leads to nonzero crystalline density wave order in each species. We furthermore show that the CSS and the SS states are present for $t_A/V \neq t_B/V$, and the latter even survives up to $t_A/V \rightarrow \infty$ or $t_B/V \rightarrow \infty$ limit. The effects induced by the variation of $U/V$ and by the imbalance of particle numbers of the two species are also explored.