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In diffusion Monte Carlo (DMC) methods, the nodes (or zeroes) of the trial wave function dictate the magnitude of the fixed-node (FN) error. Within standard DMC implementations, they emanate from short multideterminant expansions,…

Chemical Physics · Physics 2018-05-31 Anthony Scemama , Yann Garniron , Michel Caffarel , Pierre-François Loos

While Diffusion Monte Carlo (DMC) is in principle an exact stochastic method for \textit{ab initio} electronic structure calculations, in practice the fermionic sign problem necessitates the use of the fixed-node approximation and trial…

Several aspects of the recently proposed DMC-CIPSI approach consisting in using selected Configuration Interaction (SCI) approaches such as CIPSI (Configuration Interaction using a Perturbative Selection done Iteratively) to build accurate…

Chemical Physics · Physics 2017-04-20 Michel Caffarel , Thomas Applencourt , Emmanuel Giner , Anthony Scemama

By combining density-functional theory (DFT) and wave function theory (WFT) via the range separation (RS) of the interelectronic Coulomb operator, we obtain accurate fixed-node diffusion Monte Carlo (FN-DMC) energies with compact…

Chemical Physics · Physics 2020-11-04 Anthony Scemama , Emmanuel Giner , Anouar Benali , Pierre-François Loos

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 explore the use in quantum Monte Carlo (QMC) of trial wave functions consisting of a Jastrow factor multiplied by a truncated configuration-interaction (CI) expansion in Slater determinants obtained from a CI perturbatively selected…

Chemical Physics · Physics 2016-01-25 Emmanuel Giner , Roland Assaraf , Julien Toulouse

Quantum Monte Carlo (QMC) methods are some of the most accurate methods for simulating correlated electronic systems. We investigate the compatibility, strengths and weaknesses of two such methods, namely, diffusion Monte Carlo (DMC) and…

Computational Physics · Physics 2020-10-14 Fionn D. Malone , Anouar Benali , Miguel A. Morales , Michel Caffarel , P. R. C. Kent , Luke Shulenburger

The accuracy and efficiency of ab-initio quantum Monte Carlo (QMC) algorithms benefits greatly from compact variational trial wave functions that accurately reproduce ground state properties of a system. We investigate the possibility of…

Materials Science · Physics 2019-01-30 Shivesh Pathak , Lucas K. Wagner

Fixed-node diffusion Monte Carlo (DMC) is a stochastic algorithm for finding the lowest energy many-fermion wave function with the same nodal surface as a chosen trial function. It has proved itself among the most accurate methods available…

Condensed Matter · Physics 2009-10-31 W. M. C. Foulkes , Randolph Q. Hood , R. J. Needs

Fixed node diffusion quantum Monte Carlo (FN-DMC) is an increasingly used computational approach for investigating the electronic structure of molecules, solids, and surfaces with controllable accuracy. It stands out among equally accurate…

Computational Physics · Physics 2019-10-03 Andrea Zen , Jan Gerit Brandenburg , Angelos Michaelides , Dario Alfè

We develop a formalism and present an algorithm for optimization of the trial wave-function used in fixed-node diffusion quantum Monte Carlo (DMC) methods. We take advantage of a basic property of the walker configuration distribution…

Strongly Correlated Electrons · Physics 2015-05-13 Fernando A. Reboredo , Randolph Q. Hood , Paul R. C. Kent

Fixed-node diffusion Monte Carlo (FNDMC) is a stochastic quantum many-body method that has a great potential in electronic structure theory. We examine how FNDMC satisfies exact constraints, linearity and derivative discontinuity of total…

Chemical Physics · Physics 2019-10-16 Matej Ditte , Matus Dubecky

Diffusion Monte Carlo (DMC) based on fixed-node approximation has enjoyed significant developments in the past decades and become one of the go-to methods when accurate ground state energy of molecules and materials is needed. The remaining…

Chemical Physics · Physics 2023-08-07 Weiluo Ren , Weizhong Fu , Xiaojie Wu , Ji Chen

We present accurate nonrelativistic ground-state energies of the transition metal atoms of the 3d series calculated with Fixed-Node Diffusion Monte Carlo (FN-DMC). Selected multi-determinantal expansions obtained with the CIPSI method…

Chemical Physics · Physics 2016-07-25 A. Scemama , T. Applencourt , E. Giner , M. Caffarel

Diffusion Monte Carlo (DMC) is an exact technique to project out the ground state (GS) of a Hamiltonian. Since the GS is always bosonic, in fermionic systems the projection needs to be carried out while imposing anti-symmetric constraints,…

Computational Physics · Physics 2025-01-08 Kousuke Nakano , Sandro Sorella , Dario Alfè , Andrea Zen

We study several aspects of the recently introduced fixed-phase spin-orbit diffusion Monte Carlo (FPSODMC) method, in particular, its relation to the fixed-node method and its potential use as a general approach for electronic structure…

Computational Physics · Physics 2017-10-18 Cody A. Melton , Lubos Mitas

Reliable theoretical predictions of noncovalent interaction energies, which are important e.g. in drug-design and hydrogen-storage applications, belong to longstanding challenges of contemporary quantum chemistry. In this respect, the…

Chemical Physics · Physics 2016-06-06 Matúš Dubecký , René Derian , Petr Jurečka , Lubos Mitas , Pavel Hobza , Michal Otyepka

The dissociation energies of four transition metal dimers are determined using diffusion Monte Carlo. The Jastrow, CI, and molecular orbital parameters of the wave function are both partially and fully optimized with respect to the…

Chemical Physics · Physics 2019-09-06 Jil Ludovicy , Kaveh Haghighi Mood , Arne Lüchow

Due to their diverse nature, the faithful description of excited states within electronic structure theory methods remains one of the grand challenges of modern theoretical chemistry. Quantum Monte Carlo (QMC) methods have been applied very…

Chemical Physics · Physics 2020-06-05 Anthony Scemama , Michel Caffarel , Anouar Benali , Denis Jacquemin , Pierre-François Loos
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