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Quantum Monte Carlo (QMC) is a powerful method to calculate accurate energies and forces for molecular systems. In this work, we demonstrate how we can obtain accurate QMC forces for the fluxional ethanol molecule at room temperature by…

We employ quantum Monte Carlo to obtain chemically accurate vertical and adiabatic excitation energies, and equilibrium excited-state structures for the small, yet challenging, formaldehyde and thioformaldehyde molecules. A key ingredient…

Computational Physics · Physics 2019-08-02 Monika Dash , Jonas Feldt , Saverio Moroni , Anthony Scemama , Claudia Filippi

We present a study of spin-unpolarized and spin-polarized two-dimensional uniform electron liquids using variational and diffusion quantum Monte Carlo (VMC and DMC) methods with Slater-Jastrow-backflow trial wave functions. Ground-state VMC…

Strongly Correlated Electrons · Physics 2025-11-11 Sam Azadi , N. D. Drummond , S. M. Vinko

We consider the use in quantum Monte Carlo calculations of two types of valence bond wave functions based on strictly localized active orbitals, namely valence bond self-consistent-field (VBSCF) and breathing-orbital valence bond (BOVB)…

Chemical Physics · Physics 2011-03-14 Benoît Braïda , Julien Toulouse , Michel Caffarel , C. J. Umrigar

The Diffusion Monte Carlo method is devoted to the computation of electronic ground-state energies of molecules. In this paper, we focus on implementations of this method which consist in exploring the configuration space with a {\bf fixed}…

Numerical Analysis · Mathematics 2007-05-23 Tony Lelievre , Mohamed El Makrini , Benjamin Jourdain

Employing a classical density-functional description of liquid environments, we introduce a rigorous method for the diffusion quantum Monte Carlo calculation of free energies and thermodynamic averages of solvated systems that requires…

Within Full Configuration Interaction Quantum Monte Carlo, we investigate how the statistical error behaves as a function of the parameters which control the stochastic sampling. We define the inefficiency as a measure of the statistical…

Chemical Physics · Physics 2016-03-15 W. A. Vigor , J. S. Spencer , M. J. Bearpark , A. J. W. Thom

We develop a quantum Monte Carlo method for many fermions that allows the use of any one-particle basis. It projects out the ground state by random walks in the space of Slater determinants. An approximate approach is formulated to control…

Condensed Matter · Physics 2009-02-20 Shiwei Zhang , Henry Krakauer

A self-contained and tutorial presentation of the diffusion Monte Carlo method for determining the ground state energy and wave function of quantum systems is provided. First, the theoretical basis of the method is derived and then a…

Computational Physics · Physics 2009-10-30 Ioan Kosztin , Byron Faber , Klaus Schulten

Herein, we report accurate atomization energy calculations for 55 molecules in the Gaussian-2 (G2) set using lattice regularized diffusion Monte Carlo (LRDMC). We compare the Jastrow-Slater determinant ansatz with a more flexible JsAGPs…

Chemical Physics · Physics 2023-04-19 Abhishek Raghav , Ryo Maezono , Kenta Hongo , Sandro Sorella , Kousuke Nakano

We develop a formalism to directly evaluate the matrix of force constants within a Quantum Monte Carlo calculation. We utilize the matrix of force constants to accurately relax the positions of atoms in molecules and determine their…

Computational Physics · Physics 2020-04-06 Yu Yang Fredrik Liu , Bartholomew Andrews , Gareth J. Conduit

A quantum Monte Carlo method of determining Jastrow-Slater wave functions for which the energy is stationary with respect to variations in the single-particle orbitals is presented. A potential is determined by a least-squares fitting of…

Condensed Matter · Physics 2007-05-23 Stephen Fahy , Claudia Filippi

Real-space quantum Monte Carlo is used to calculate the total atomization energy of benzene. In contrast to orbital-space methods common in quantum chemistry, real-space methods allow results at near the complete-basis-set limit to be…

Strongly Correlated Electrons · Physics 2021-07-21 Iliya Sabzevari , Sandeep Sharma

We present high-accuracy correlated calculations of small Si$_x$H$_y$ molecular systems both in the ground and excited states. We employ quantum Monte Carlo (QMC) together with a variety of many-body wave function approaches based on basis…

Chemical Physics · Physics 2020-10-21 Guangming Wang , Abdulgani Annaberdiyev , Lubos Mitas

All-electron Fixed-node Diffusion Monte Carlo (FN-DMC) calculations for the nonrelativistic ground-state energy of the water molecule at equilibrium geometry are presented. The determinantal part of the trial wavefunction is obtained from a…

Chemical Physics · Physics 2016-05-25 Michel Caffarel , Thomas Applencourt , Emmanuel Giner , Anthony Scemama

We study three wave function optimization methods based on energy minimization in a variational Monte Carlo framework: the Newton, linear and perturbative methods. In the Newton method, the parameter variations are calculated from the…

Chemical Physics · Physics 2015-06-26 Julien Toulouse , C. J. Umrigar

Quantum Monte Carlo methods are used to calculate various ground state properties of charged bosons in two dimensions, throughout the whole density range where the fluid phase is stable. Wigner crystallization is predicted at $r_s\simeq…

Condensed Matter · Physics 2018-05-01 S. De Palo , S. Conti , S. Moroni

We report diffusion quantum Monte Carlo calculations of three-dimensional Wigner crystals in the density range r_s=100-150. We have tested different types of orbital for use in the approximate wave functions but none improve upon the simple…

Strongly Correlated Electrons · Physics 2008-01-03 N. D. Drummond , Z. Radnai , J. R. Trail , M. D. Towler , R. J. Needs

We present and motivate an efficient way to include orbital dependent many--body correlations in trial wave function of real--space Quantum Monte Carlo methods for use in electronic structure calculations. We apply our new…

Computational Physics · Physics 2019-10-17 Markus Holzmann , Saverio Moroni

Computation of ionic forces using quantum Monte Carlo methods has long been a challenge. We introduce a simple procedure, based on known properties of physical electronic densities, to make the variance of the Hellmann-Feynman estimator…

Computational Physics · Physics 2007-05-23 Simone Chiesa , David Ceperley , Shiwei Zhang