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Stochastic Formulation of the Resolution of Identity: Application to Second Order Møller–Plesset Perturbation Theory

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [3];  [4];  [5]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of California, Los Angeles, CA (United States)
  4. Hebrew Univ. of Jerusalem (Israel). Fritz Harber Center for Molecular Dynamics
  5. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Tel Aviv Univ. (Israel), The Sacler Center for Computational Molecular Science
+ Show Author Affiliations

A stochastic orbital approach to the resolution of identity (RI) approximation for 4-index electron repulsion integrals (ERIs) is presented. The stochastic RI-ERIs are then applied to second order Møller–Plesset perturbation theory (MP2) utilizing a multiple stochastic orbital approach. The introduction of multiple stochastic orbitals results in an O(NAO3) scaling for both the stochastic RI-ERIs and stochastic RI-MP2, NAO being the number of basis functions. For a range of water clusters we demonstrate that this method exhibits a small prefactor and observed scalings of O(Ne2.4) for total energies and O(Ne3.1) for forces (Ne being the number of correlated electrons), outperforming MP2 for clusters with as few as 21 water molecules.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543624
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 10 Vol. 13; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Laplace transformed MP2 for three dimensional periodic materials using stochastic orbitals in the plane wave basis and correlated sampling journal February 2018
Stochastic resolution of identity second-order Matsubara Green’s function theory journal July 2019
Stochastic density functional theory at finite temperatures journal March 2018
Laplace transformed MP2 for three dimensional periodic materials using stochastic orbitals in the plane wave basis and correlated sampling text January 2017

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