Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions
Abstract
With the aim of systematically comparing two popular approaches to density functional theory–all-electron calculations with local basis sets, and periodic calculations employing plane wave basis sets and norm-conserving pseudopotentials–we have computed complete-basis binding energies across the S22 set of intermolecular interactions, a dataset consisting of noncovalent interactions of small- and medium-sized molecules containing first- and second-row atoms, using the Troullier-Martins norm-conserving pseudopotentials with SPW92, a local spin-density approximation; and PBE, a generalised gradient approximation. Here, we have found that it is challenging to reach the basis set limit with these periodic calculations; for the methods and systems examined, a minimum vacuum distance of 30 Å between a system and its nearest images is necessary–unless some form of dipole correction is employed–as is a kinetic energy cutoff of at least 80 Ry. The trends in convergence with respect to vacuum size and kinetic energy cutoff are largely independent of the level of density functional approximation employed. A sense of the impact of each hyperparameter on basis set error provides a foundation for ensuring quality calculations in future studies and allows us to quantify the basis set errors incurred in existing studies on similar systems.
- Authors:
-
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
- OSTI Identifier:
- 1814759
- Grant/Contract Number:
- AC02-05CH11231; FG02-12ER16362
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Molecular Physics
- Additional Journal Information:
- Journal Volume: 117; Journal Issue: 9-12; Journal ID: ISSN 0026-8976
- Publisher:
- Taylor & Francis
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; Intermolecular interactions; density functional theory; basis set limit; plane waves; atomic orbitals
Citation Formats
Witte, Jonathon, Neaton, Jeffrey B., and Head-Gordon, Martin. Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions. United States: N. p., 2018.
Web. doi:10.1080/00268976.2018.1542164.
Witte, Jonathon, Neaton, Jeffrey B., & Head-Gordon, Martin. Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions. United States. https://doi.org/10.1080/00268976.2018.1542164
Witte, Jonathon, Neaton, Jeffrey B., and Head-Gordon, Martin. Thu .
"Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions". United States. https://doi.org/10.1080/00268976.2018.1542164. https://www.osti.gov/servlets/purl/1814759.
@article{osti_1814759,
title = {Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions},
author = {Witte, Jonathon and Neaton, Jeffrey B. and Head-Gordon, Martin},
abstractNote = {With the aim of systematically comparing two popular approaches to density functional theory–all-electron calculations with local basis sets, and periodic calculations employing plane wave basis sets and norm-conserving pseudopotentials–we have computed complete-basis binding energies across the S22 set of intermolecular interactions, a dataset consisting of noncovalent interactions of small- and medium-sized molecules containing first- and second-row atoms, using the Troullier-Martins norm-conserving pseudopotentials with SPW92, a local spin-density approximation; and PBE, a generalised gradient approximation. Here, we have found that it is challenging to reach the basis set limit with these periodic calculations; for the methods and systems examined, a minimum vacuum distance of 30 Å between a system and its nearest images is necessary–unless some form of dipole correction is employed–as is a kinetic energy cutoff of at least 80 Ry. The trends in convergence with respect to vacuum size and kinetic energy cutoff are largely independent of the level of density functional approximation employed. A sense of the impact of each hyperparameter on basis set error provides a foundation for ensuring quality calculations in future studies and allows us to quantify the basis set errors incurred in existing studies on similar systems.},
doi = {10.1080/00268976.2018.1542164},
journal = {Molecular Physics},
number = 9-12,
volume = 117,
place = {United States},
year = {Thu Nov 08 00:00:00 EST 2018},
month = {Thu Nov 08 00:00:00 EST 2018}
}
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