Back to Search
Start Over
Sampling the reciprocal Coulomb potential in finite anisotropic cells.
- Source :
-
The Journal of chemical physics [J Chem Phys] 2024 Feb 07; Vol. 160 (5). - Publication Year :
- 2024
-
Abstract
- We present a robust strategy to numerically sample the Coulomb potential in reciprocal space for periodic Born-von Karman cells of general shape. Our approach tackles two common issues of plane-wave based implementations of Coulomb integrals under periodic boundary conditions: the treatment of the singularity at the Brillouin-zone center and discretization errors, which can cause severe convergence problems in anisotropic cells, necessary for the calculation of low-dimensional systems. We apply our strategy to the Hartree-Fock and coupled cluster (CC) theories and discuss the consequences of different sampling strategies on different theories. We show that sampling the Coulomb potential via the widely used probe-charge Ewald method is unsuitable for CC calculations in anisotropic cells. To demonstrate the applicability of our developed approach, we study two representative, low-dimensional use cases: the infinite carbon chain, for which we report the first periodic CCSD(T) potential energy surface, and a surface slab of lithium hydride, for which we demonstrate the impact of different sampling strategies for calculating surface energies. We find that our Coulomb sampling strategy serves as a vital solution, addressing the critical need for improved accuracy in plane-wave based CC calculations for low-dimensional systems.<br /> (© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)
Details
- Language :
- English
- ISSN :
- 1089-7690
- Volume :
- 160
- Issue :
- 5
- Database :
- MEDLINE
- Journal :
- The Journal of chemical physics
- Publication Type :
- Academic Journal
- Accession number :
- 38310470
- Full Text :
- https://doi.org/10.1063/5.0182729