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Carlo Pierleoni

Publications and source records attributed to Carlo Pierleoni.

54 records · Page 3Linked to original sources
arXiv2011

Free energy methods in Coupled Electron Ion Monte Carlo

Recent progress in simulation methodologies and in computer power allow first principle simulations of condensed systems with Born-Oppenheimer electronic energies obtained by Quantum Monte Carlo methods. Computing free energies and therefore getting a quantitative determination of phase diagrams is one step more demanding in terms of computer resources. In this paper we derive a general relation to compute the free energy of an ab-initio model with Reptation Quantum Monte Carlo (RQMC) energies from the knowledge of the free energy of the same ab-initio model in which the electronic energies are computed by the less demanding but less accurate Variational Monte Carlo (VMC) method. Moreover we devise a procedure to correct transition lines based on the use of the new relation. In order to illustrate the procedure, we consider the liquid-liquid phase transition in hydrogen, a first order transition between a lower pressure, molecular and insulating phase and a higher pressure, partially dissociated and conducting phase. We provide new results along the T = 600K isotherm across the phase transition and find good agreement between the transition pressure and specific volumes at coexistence for the model with RQMC accuracy between the prediction of our procedure and the values that can be directly inferred from the observed plateau in the pressure-volume curve along the isotherm. This work paves the way for future use of VMC in first principle simulations of high pressure hydrogen, an essential simplification when considering larger system sizes or quantum proton effects by Path Integral Monte Carlo methods.

cond-mat.stat-mech↗
arXiv2011

The momentum distribution of the homogeneous electron gas

We calculate the off-diagonal density matrix of the homogeneous electron gas at zero temperature using unbiased Reptation Monte Carlo for various densities and extrapolate the momentum distribution, and the kinetic and potential energies to the thermodynamic limit. Our results on the renormalization factor allows us to validate approximate G_0W_0 calculations concerning quasiparticle properties over a broad density region (1 <= r_s <= 10) and show that near the Fermi surface, vertex corrections and self-consistency aspects almost cancel each other out.

cond-mat.str-el↗
arXiv2010

Electrical conductivity of high-pressure liquid hydrogen by quantum Monte Carlo methods

We compute the electrical conductivity for liquid hydrogen at high pressure using quantum Monte Carlo. The method uses Coupled Electron-Ion Monte Carlo to generate configurations of liquid hydrogen. For each configuration correlated sampling of electrons is performed in order to calculate a set of lowest many-body eigenstates and current-current correlation functions of the system, which are summed over in the many-body Kubo formula to give AC electrical conductivity directly. The extrapolated DC conductivity at 3000 K for several densities shows a liquid semiconductor to liquid-metal transition at high pressure. Our results are in good agreement with shock-wave data.

cond-mat.str-el↗
arXiv2009

Equation of state of metallic hydrogen from Coupled Electron-Ion Monte Carlo simulations

We present a study of hydrogen at pressures higher than molecular dissociation using the Coupled Electron-Ion Monte Carlo method. These calculations use the accurate Reptation Quantum Monte Carlo method to estimate the electronic energy and pressure while doing a Monte Carlo simulation of the protons. In addition to presenting simulation results for the equation of state over a large region of phase space, we report the free energy obtained by thermodynamic integration. We find very good agreement with DFT calculations for pressures beyond 600 GPa and densities above $ρ=1.4 g/cm^3$. Both thermodynamic as well as structural properties are accurately reproduced by DFT calculations. This agreement gives a strong support to the different approximations employed in DFT, specifically the approximate exchange-correlation potential and the use of pseudopotentials for the range of densities considered. We find disagreement with chemical models, which suggests a reinvestigation of planetary models, previously constructed using the Saumon-Chabrier-Van Horn equations of state.

cond-mat.mtrl-sci↗
arXiv2008

Bulk viscosity of the Lennard-Jones system at the triple point by dynamical Non Equilibrium Molecular Dynamics

Non-equilibrium Molecular Dynamics (NEMD) calculations of the bulk viscosity of the triple point Lennard-Jones fluid are performed with the aim of investigating the origin of the observed disagreement between Green-Kubo estimates and previous NEMD data. We show that a careful application of the Doll's perturbation field, the dynamical NEMD method, the instantaneous form of the perturbation and the "subtraction technique" provides a NEMD estimate of the bulk viscosity at zero field in full agreement with the value obtained by the Green-Kubo formula. As previously reported for the shear viscosity, we find that the bulk viscosity exhibits a large linear regime with the field intensity which confirms the Lennard-Jones fluid as a genuine Newtonian fluid even at triple point.

cond-mat.soft↗
arXiv2007

Trial wave functions for High-Pressure Metallic Hydrogen

Many body trial wave functions are the key ingredient for accurate Quantum Monte Carlo estimates of total electronic energies in many electron systems. In the Coupled Electron-Ion Monte Carlo method, the accuracy of the trial function must be conjugated with the efficiency of its evaluation. We report recent progress in trial wave functions for metallic hydrogen implemented in the Coupled Electron-Ion Monte Carlo method. We describe and characterize several types of trial functions of increasing complexity in the range of the coupling parameter $1.0 \leq r_s \leq1.55$. We report wave function comparisons for disordered protonic configurations and preliminary results for thermal averages.

physics.comp-ph↗
arXiv2007

A multi-blob representation of semi-dilute polymer solutions

A coarse-grained multi-blob description of polymer solutions is presented, based on soft, transferable effective interactions between bonded and non-bonded blobs. The number of blobs is chosen such that the blob density does not exceed their overlap threshold, allowing polymer concentrations to be explored deep into the semi-dilute regime. This quantitative multi-blob description is shown to preserve known scaling laws of polymer solutions and provides accurate estimates of amplitudes, while leading to orders of magnitude increase of simulation efficiency and allowing analytic calculations of structural and thermodynamic properties.

cond-mat.soft↗
arXiv2006

Quantum Monte Carlo Simulation of the High-Pressure Molecular-Atomic Crossover in Fluid Hydrogen

A first-order liquid-liquid phase transition in high-pressure hydrogen between molecular and atomic fluid phases has been predicted in computer simulations using ab initio molecular dynamics approaches. However, experiments indicate that molecular dissociation may occur through a continuous crossover rather than a first-order transition. Here we study the nature of molecular dissociation in fluid hydrogen using an alternative simulation technique in which electronic correlation is computed within quantum Monte Carlo, the so-called Coupled Electron Ion Monte Carlo (CEIMC) method. We find no evidence for a first-order liquid-liquid phase transition.

cond-mat.stat-mech↗
arXiv2006

Multi-scale coarse-graining of diblock copolymer self-assembly: from monomers to ordered micelles

Starting from a microscopic lattice model, we investigate clustering, micellization and micelle ordering in semi-dilute solutions of AB diblock copolymers in a selective solvent. To bridge the gap in length scales, from monomers to ordered micellar structures, we implement a two-step coarse graining strategy, whereby the AB copolymers are mapped onto ``ultrasoft'' dumbells with monomer-averaged effective interactions between the centres of mass of the blocks. Monte Carlo simulations of this coarse-grained model yield clear-cut evidence for self-assembly into micelles with a mean aggregation number n of roughly 100 beyond a critical concentration. At a slightly higher concentration the micelles spontaneously undergo a disorder-order transition to a cubic phase. We determine the effective potential between these micelles from first principles.

cond-mat.soft↗
arXiv2005

Computational methods in Coupled Electron-Ion Monte Carlo

In the last few years we have been developing a Monte Carlo simulation method to cope with systems of many electrons and ions in the Born-Oppenheimer (BO) approximation, the Coupled Electron-Ion Monte Carlo Method (CEIMC). Electronic properties in CEIMC are computed by Quantum Monte Carlo (QMC) rather than by Density Functional Theory (DFT) based techniques. CEIMC can, in principle, overcome some of the limitations of the present DFT based ab initio dynamical methods. Application of the new method to high pressure metallic hydrogen has recently appeared. In this paper we present a new sampling algorithm that we have developed in the framework of the Reptation Quantum Monte Carlo (RQMC) method chosen to sample the electronic degrees of freedom, thereby improving its efficiency. Moreover, we show here that, at least for the case of metallic hydrogen, variational estimates of the electronic energies lead to an accurate sampling of the proton degrees of freedom.

physics.comp-ph↗
arXiv2004

Coupled Electron Ion Monte Carlo Calculations of Atomic Hydrogen

We present a new Monte Carlo method which couples Path Integral for finite temperature protons with Quantum Monte Carlo for ground state electrons, and we apply it to metallic hydrogen for pressures beyond molecular dissociation. This method fills the gap between high temperature electron-proton Path Integral and ground state Diffusion Monte Carlo methods. Our data exhibit more structure and higher melting temperatures of the proton crystal than Car-Parrinello Molecular Dynamics results using LDA. We further discuss the quantum motion of the protons and the zero temperature limit.

cond-mat.stat-mech↗
arXiv2004

Coupled Electron Ion Monte Carlo Calculations of Dense Metallic Hydrogen

We present a new Monte Carlo method which couples Path Integral for finite temperature protons with Quantum Monte Carlo for ground state electrons, and we apply it to metallic hydrogen for pressures beyond molecular dissociation. We report data for the equation of state for temperatures across the melting of the proton crystal. Our data exhibit more structure and higher melting temperatures of the proton crystal than Car-Parrinello Molecular Dynamics results. This method fills the gap between high temperature electron-proton Path Integral and ground state Diffusion Monte Carlo methods.

physics.comp-ph↗
arXiv2002

Single chain elasticity and thermoelasticity of polyethylene

Single-chain elasticity of polyethylene at $θ$ point up to 90% of stretching with respect to its contour length is computed by Monte-Carlo simulation of an atomistic model in continuous space. The elasticity law together with the free-energy and the internal energy variations with stretching are found to be very well represented by the wormlike chain model up to 65% of the chain elongation, provided the persistence length is treated as a temperature dependent parameter. Beyond this value of elongation simple ideal chain models are not able to describe the Monte Carlo data in a thermodynamic consistent way. This study reinforces the use of the wormlike chain model to interpret experimental data on the elasticity of synthetic polymers in the finite extensibility regime, provided the chain is not yet in its fully stretched regime. Specific solvent effects on the elasticity law and the partition between energetic and entropic contributions to single chain elasticity are investigated.

cond-mat.soft↗
arXiv2002

The Coupled Electronic-Ionic Monte Carlo Simulation Method

Quantum Monte Carlo (QMC) methods such as Variational Monte Carlo, Diffusion Monte Carlo or Path Integral Monte Carlo are the most accurate and general methods for computing total electronic energies. We will review methods we have developed to perform QMC for the electrons coupled to a classical Monte Carlo simulation of the ions. In this method, one estimates the Born-Oppenheimer energy E(Z) where Z represents the ionic degrees of freedom. That estimate of the energy is used in a Metropolis simulation of the ionic degrees of freedom. Important aspects of this method are how to deal with the noise, which QMC method and which trial function to use, how to deal with generalized boundary conditions on the wave function so as to reduce the finite size effects. We discuss some advantages of the CEIMC method concerning how the quantum effects of the ionic degrees of freedom can be included and how the boundary conditions can be integrated over. Using these methods, we have performed simulations of liquid H2 and metallic H on a parallel computer.

physics.comp-ph↗
arXiv2000

Excluded volume effects on the structure of a linear polymer under shear flow

The effect of excluded volume interactions on the structure of a polymer in shear flow is investigated by Brownian Dynamics simulations for chains with size $30\leq N\leq 300$. The main results concern the structure factor $S({\bf q})$ of chains of N=300 Kuhn segments, observed at a reduced shear rate $β=\dotγτ=3.2$, where $\dotγ$ is the bare shear rate and $τ$ is the longest relaxation time of the chain. At low q, where anisotropic global deformation is probed, the chain form factor is shown to match the form factor of the continuous Rouse model under shear at the same reduced shear rate, computed here for the first time in a wide range of wave vectors. At high q, the chain structure factor evolves towards the isotropic equilibrium power law $q^{-1/ν}$ typical of self-avoiding walk statistics. The matching between excluded volume and ideal chains at small q, and the excluded volume power law behavior at large q are observed for ${\bf q}$ orthogonal to the main elongation axis but not yet for ${\bf q}$ along the elongation direction itself, as a result of interferences with finite extensibility effects. Our simulations support the existence of anisotropic shear blobs for polymers in good solvent under shear flow for $β>1$ provided chains are sufficiently long.

cond-mat.soft↗
arXiv2000

The induced charge in a Frohlich polaron: Sum rule and spatial extent

Within the path integral formalism, we derive exact expressions for correlation functions measuring the lattice charge induced by an electron and associated polarization in Frohlich polaron problem. We prove that a sum rule for the total induced charge, already obtained within approximated approaches is indeed exact. As a consequence the total induced charge is shown rigorously to be temperature independent. In addition we perform path integral Monte Carlo calculations of the correlation functions and we compare with variational results based on Feynman method. As the temperature increases the polaron radius decreases. On the other hand at high temperatures the electron motion is not hindered by the lattice. These apparently contradictory results are discussed.

cond-mat.str-el↗
arXiv1997

On the signature of tensile blobs in the scattering function of a stretched polymer

We present Monte Carlo data for a linear chain with excluded volume subjected to a uniform stretching. Simulation of long chains (up to 6000 beads) at high stretching allows us to observe the signature of tensile blobs as a crossover in the scaling behavior of the chain scattering function for wave vectors perpendicular to stretching. These results and corresponding ones in the stretching direction allow us to verify for the first time Pincus prediction on scaling inside blobs. Outside blobs, the scattering function is well described by the Debye function for a stretched ideal chain.

cond-mat.soft↗