We describe an efficient projection-based real-space implementation of the nonlocal single-determinant exchange operator. Through a matrix representation of the projected operator, we show that this scheme works equally well for both occupied and virtual states. Our scheme reaches a speedup of 2 orders of magnitude and has no significant loss of accuracy compared to an implementation of the full nonlocal single-determinant exchange operator. We find excellent agreement upon comparing Hartree-Fock eigenvalues, dipoles, and polarizabilities of selected molecules calculated using our method to values in the literature. To illustrate the efficiency of this scheme we perform calculations on systems with up to 240 carbon atoms.
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http://dx.doi.org/10.1021/acs.jctc.6b00376 | DOI Listing |
J Chem Phys
July 2017
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
The necessarily approximate evaluation of non-local pseudopotentials in diffusion Monte Carlo (DMC) introduces localization errors. We estimate these errors for two families of non-local pseudopotentials for the first-row transition metal atoms Sc-Zn using an extrapolation scheme and multideterminant wavefunctions. Sensitivities of the error in the DMC energies to the Jastrow factor are used to estimate the quality of two sets of pseudopotentials with respect to locality error reduction.
View Article and Find Full Text PDFJ Chem Theory Comput
August 2016
Department of Physical Electronics, Tel-Aviv University, Tel-Aviv 69978, Israel.
We describe an efficient projection-based real-space implementation of the nonlocal single-determinant exchange operator. Through a matrix representation of the projected operator, we show that this scheme works equally well for both occupied and virtual states. Our scheme reaches a speedup of 2 orders of magnitude and has no significant loss of accuracy compared to an implementation of the full nonlocal single-determinant exchange operator.
View Article and Find Full Text PDFJ Chem Phys
August 2007
Department of Chemistry, Rice University, Houston, Texas 77005, USA.
An effective local potential (ELP) is a multiplicative operator whose deviation from a given nonlocal potential has the smallest variance evaluated with a prescribed single-determinant wave function. ELPs are useful in density functional theory as alternatives to optimized effective potentials (OEPs) because they do not require special treatment in finite basis set calculations as OEPs do. We generalize the idea of variance-minimizing potentials by introducing the concept of a self-consistent ELP (SCELP), a local potential whose deviation from its nonlocal counterpart has the smallest variance in terms of its own Kohn-Sham orbitals.
View Article and Find Full Text PDFPhys Rev Lett
April 2003
Department of Physics, College of William and Mary, Williamsburg, Virginia 23187-8795, USA.
We develop a quantum Monte Carlo method for many fermions using random walks in the space of Slater determinants. An approximate approach is formulated with a trial wave function |Psi(T)> to control the phase problem. Using a plane-wave basis and nonlocal pseudopotentials, we apply the method to Be, Si, and P atoms and dimers, and to bulk Si supercells.
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