Energy decomposition analysis method for metallic systems
Energy decomposition analysis method for metallic systems
In this work, we present the first extension of an energy decomposition analysis (EDA) method to metallic systems. We extend the theory of our Hybrid Absolutely Localized Molecular Orbitals (HALMO) EDA to take into account that molecular orbitals in metallic systems are partially occupied, which is done by weighted orthogonalization (WO) of the molecular orbitals using their associated fractional occupancies as weights in the construction of the projection operators. These operators are needed for the self-consistent field for molecular interaction (SCF MI) computation of the polarization-energy contribution to the interaction. The method gives more weight to orbitals that have higher occupancies and treats each fragment as metallic. The resulting HALMO EDA for metallic systems naturally reduces to the insulator version and produces the same results when applied to an insulating system. We present the theory and implementation of our new approach, and we demonstrate it with sample calculations of relevance to industrial materials. This work provides a new EDA paradigm and tool for the study and analysis of interactions in metallic systems within large-scale DFT calculations.
1702-1711
Chen, Han
3f0c8bfb-38cc-41ad-aa92-6f77bfa0897b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Chen, Han
3f0c8bfb-38cc-41ad-aa92-6f77bfa0897b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Chen, Han and Skylaris, Chris-Kriton
(2021)
Energy decomposition analysis method for metallic systems.
Physical Chemistry Chemical Physics, 2022 (24), .
(doi:10.1039/D1CP05112A).
Abstract
In this work, we present the first extension of an energy decomposition analysis (EDA) method to metallic systems. We extend the theory of our Hybrid Absolutely Localized Molecular Orbitals (HALMO) EDA to take into account that molecular orbitals in metallic systems are partially occupied, which is done by weighted orthogonalization (WO) of the molecular orbitals using their associated fractional occupancies as weights in the construction of the projection operators. These operators are needed for the self-consistent field for molecular interaction (SCF MI) computation of the polarization-energy contribution to the interaction. The method gives more weight to orbitals that have higher occupancies and treats each fragment as metallic. The resulting HALMO EDA for metallic systems naturally reduces to the insulator version and produces the same results when applied to an insulating system. We present the theory and implementation of our new approach, and we demonstrate it with sample calculations of relevance to industrial materials. This work provides a new EDA paradigm and tool for the study and analysis of interactions in metallic systems within large-scale DFT calculations.
Text
han_paper2_2021_12_09
- Accepted Manuscript
Text
d1cp05112a
- Version of Record
More information
Accepted/In Press date: 17 December 2021
e-pub ahead of print date: 21 December 2021
Additional Information:
The authors acknowledge the use of the IRIDIS 5 High Performance Computing Facility, and associated support services at the University of Southampton. The authors are also grateful for computational support from the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/T022213/1). This work is part of University of Southampton's Centre for Doctoral Training in Next Generation Computational Modelling (NGCM).
Identifiers
Local EPrints ID: 454423
URI: http://eprints.soton.ac.uk/id/eprint/454423
ISSN: 1463-9076
PURE UUID: 2eb5808f-df35-473a-bc31-8ded9ced65d9
Catalogue record
Date deposited: 09 Feb 2022 17:35
Last modified: 17 Mar 2024 03:07
Export record
Altmetrics
Contributors
Author:
Han Chen
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics