Efficient Computation of the Hartree-Fock Exchange in Real-Space with Projection Operators.

J Chem Theory Comput

Department of Physical Electronics, Tel-Aviv University, Tel-Aviv 69978, Israel.

Published: August 2016

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.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.jctc.6b00376DOI Listing

Publication Analysis

Top Keywords

nonlocal single-determinant
8
single-determinant exchange
8
exchange operator
8
efficient computation
4
computation hartree-fock
4
hartree-fock exchange
4
exchange real-space
4
real-space projection
4
projection operators
4
operators describe
4

Similar Publications

Quantitative estimation of localization errors of 3d transition metal pseudopotentials in diffusion Monte Carlo.

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 PDF

Efficient Computation of the Hartree-Fock Exchange in Real-Space with Projection Operators.

J 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 PDF

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 PDF

Quantum Monte Carlo method using phase-free random walks with slater determinants.

Phys 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.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!