Taming the fixed-node error in diffusion Monte Carlo via range separation - Archive ouverte HAL
Article Dans Une Revue The Journal of Chemical Physics Année : 2020

Taming the fixed-node error in diffusion Monte Carlo via range separation

Résumé

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 multi-determinant trial wave functions. In particular, we combine here short-range exchange-correlation functionals with a flavor of selected configuration interaction (SCI) known as \emph{configuration interaction using a perturbative selection made iteratively} (CIPSI), a scheme that we label RS-DFT-CIPSI. One of the take-home messages of the present study is that RS-DFT-CIPSI trial wave functions yield lower fixed-node energies with more compact multi-determinant expansions than CIPSI, especially for small basis sets. Indeed, as the CIPSI component of RS-DFT-CIPSI is relieved from describing the short-range part of the correlation hole around the electron-electron coalescence points, the number of determinants in the trial wave function required to reach a given accuracy is significantly reduced as compared to a conventional CIPSI calculation. Importantly, by performing various numerical experiments, we evidence that the RS-DFT scheme essentially plays the role of a simple Jastrow factor by mimicking short-range correlation effects, hence avoiding the burden of performing a stochastic optimization. Considering the 55 atomization energies of the Gaussian-1 benchmark set of molecules, we show that using a fixed value of $\mu=0.5$~bohr$^{-1}$ provides effective error cancellations as well as compact trial wave functions, making the present method a good candidate for the accurate description of large chemical systems.
Fichier principal
Vignette du fichier
2008.10088.pdf (550.51 Ko) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-02921286 , version 1 (03-09-2020)

Identifiants

Citer

Anthony Scemama, Emmanuel Giner, Anouar Benali, Pierre-Francois Loos. Taming the fixed-node error in diffusion Monte Carlo via range separation. The Journal of Chemical Physics, 2020, 15 (17), pp.174107. ⟨10.1063/5.0026324⟩. ⟨hal-02921286⟩
51 Consultations
82 Téléchargements

Altmetric

Partager

More