Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

Author(s)
Andreas Grüneis, James J. Shepherd, Ali Alavi, David P. Tew, George H. Booth
Abstract

We present an investigation into the use of an explicitly correlated plane wave basis for periodic wavefunction expansions at the level of second-order Møller-Plesset (MP2) perturbation theory. The convergence of the electronic correlation energy with respect to the one-electron basis set is investigated and compared to conventional MP2 theory in a finite homogeneous electron gas model. In addition to the widely used Slater-type geminal correlation factor, we also derive and investigate a novel correlation factor that we term Yukawa-Coulomb. The Yukawa-Coulomb correlation factor is motivated by analytic results for two electrons in a box and allows for a further improved convergence of the correlation energies with respect to the employed basis set. We find the combination of the infinitely delocalized plane waves and local short-ranged geminals provides a complementary, and rapidly convergent basis for the description of periodic wavefunctions. We hope that this approach will expand the scope of discrete wavefunction expansions in periodic systems.

Organisation(s)
Computational Materials Physics
External organisation(s)
University of Bristol, University of Cambridge
Journal
Journal of Chemical Physics
Volume
139
No. of pages
13
ISSN
0021-9606
DOI
https://doi.org/10.1063/1.4818753
Publication date
08-2013
Peer reviewed
Yes
Austrian Fields of Science 2012
103009 Solid state physics, 103015 Condensed matter, 103025 Quantum mechanics, 103036 Theoretical physics
Keywords
Portal url
https://ucrisportal.univie.ac.at/en/publications/e2ab1fdc-0d3c-42f4-a31c-eab12c709a39