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  4. Efficient Treatment of Correlation Energies at the Basis-Set Limit by Monte Carlo Summation of Continuum States
 
research article

Efficient Treatment of Correlation Energies at the Basis-Set Limit by Monte Carlo Summation of Continuum States

Bircher, Martin P.
•
Villard, Justin  
•
Rothlisberger, Ursula  
October 13, 2020
Journal of Chemical Theory and Computation

The calculation of electron correlation is vital for the description of atomistic phenomena in physics, chemistry, and biology. However, accurate wavefunction-based methods exhibit steep scaling and often sluggish convergence with respect to the basis set at hand. Because of their delocalization and ease of extrapolation to the basis-set limit, plane waves would be ideally suited for the calculation of basis-set limit correlation energies. However, the routine use of correlated wavefunction approaches in a plane-wave basis set is hampered by prohibitive scaling due to a large number of virtual continuum states and has not been feasible for all but the smallest systems, even if substantial computational resources are available and methods with comparably beneficial scaling, such as the Moller-Plesset perturbation theory to second order (MP2), are used. Here, we introduce a stochastic sampling of the MP2 integrand based on Monte Carlo summation over continuum orbitals, which allows for speedups of up to a factor of 1000. Given a fixed number of sampling points, the resulting algorithm is dominated by a flat scaling of similar to O(N-2). Absolute correlation energies are accurate to <0.1 kcal/mol with respect to conventional calculations for several hundreds of electrons. This allows for the calculation of unbiased basis-set limit correlation energies for systems containing hundreds of electrons with unprecedented efficiency gains based on a straightforward treatment of continuum contributions.

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Type
research article
DOI
10.1021/acs.jctc.0c00724
Web of Science ID

WOS:000580954000050

Author(s)
Bircher, Martin P.
Villard, Justin  
Rothlisberger, Ursula  
Date Issued

2020-10-13

Publisher

AMER CHEMICAL SOC

Published in
Journal of Chemical Theory and Computation
Volume

16

Issue

10

Start page

6550

End page

6559

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

plesset perturbation-theory

•

density-functional theory

•

hartree-fock

•

laplace transform

•

plane-waves

•

virtual orbitals

•

ab-initio

•

electron correlation

•

dielectric-constant

•

molecular-dynamics

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCBC  
Available on Infoscience
November 24, 2020
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/173501
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