A program system for self-consistent embedded potentials for ionic crystals
Larsson, Ernst D. LU ; Krośnicki, Marek and Veryazov, Valera LU
(2022)
In Chemical Physics
562.
- Abstract
Embedded-cluster models of crystalline solids are important to allow accurate wave function methods to be applicable to solids. The ab initio model potential method for embedding ionic solids has historically been shown to be a viable tool. While useful, the method has been limited by the need to generate such potentials for each crystal structure and the lack of a freely available program for generating ab initio model potentials. Herein, this is remedied by showcasing a new, AFL licensed, program, SCEPIC, which can be used in combination with Molcas or OpenMolcas codes to derive ab initio model potentials for ionic crystals. The applicability of ab initio model potentials derived via SCEPIC is evaluated for three simple ionic solids:... (More)
Embedded-cluster models of crystalline solids are important to allow accurate wave function methods to be applicable to solids. The ab initio model potential method for embedding ionic solids has historically been shown to be a viable tool. While useful, the method has been limited by the need to generate such potentials for each crystal structure and the lack of a freely available program for generating ab initio model potentials. Herein, this is remedied by showcasing a new, AFL licensed, program, SCEPIC, which can be used in combination with Molcas or OpenMolcas codes to derive ab initio model potentials for ionic crystals. The applicability of ab initio model potentials derived via SCEPIC is evaluated for three simple ionic solids: MgO, CaO and CaF2. The following questions are addressed: (i) the capability of the method to reproduce the density matrix from periodic density functional theory calculations, (ii) the feasibility of performing geometry optimisations, (iii) the possibility to model band gaps of insulators and (iv) the ligand-field splitting of Ni-doped MgO. Going beyond the classical restriction of parametrising ab initio model potentials only at the Hartree–Fock level-of-theory, this work additionally address the sensitivity of results to the underlying Hamiltonian used to derive the potentials. The results demonstrate that good agreement with periodic density functional theory calculations can be achieved, geometry optimisations are feasible and accurate band gaps and ligand-field splittings can be computed.
(Less)
- author
- Larsson, Ernst D.
LU
; Krośnicki, Marek
and Veryazov, Valera
LU
- organization
- publishing date
- 2022-10-01
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Ab-initio model potential, Band gaps, CASPT2, Ionic solids, Ligand-field splitting
- in
- Chemical Physics
- volume
- 562
- article number
- 111549
- pages
- 19 pages
- publisher
- Elsevier
- external identifiers
-
- scopus:85134597406
- ISSN
- 0301-0104
- DOI
- 10.1016/j.chemphys.2022.111549
- language
- English
- LU publication?
- yes
- additional info
- Publisher Copyright: © 2022 The Author(s)
- id
- 2b6afc73-ccea-465d-bcb5-c69aa14d5d0c
- date added to LUP
- 2022-08-15 12:51:14
- date last changed
- 2023-04-08 12:25:56
@article{2b6afc73-ccea-465d-bcb5-c69aa14d5d0c,
abstract = {{<p>Embedded-cluster models of crystalline solids are important to allow accurate wave function methods to be applicable to solids. The ab initio model potential method for embedding ionic solids has historically been shown to be a viable tool. While useful, the method has been limited by the need to generate such potentials for each crystal structure and the lack of a freely available program for generating ab initio model potentials. Herein, this is remedied by showcasing a new, AFL licensed, program, SCEPIC, which can be used in combination with Molcas or OpenMolcas codes to derive ab initio model potentials for ionic crystals. The applicability of ab initio model potentials derived via SCEPIC is evaluated for three simple ionic solids: MgO, CaO and CaF<sub>2</sub>. The following questions are addressed: (i) the capability of the method to reproduce the density matrix from periodic density functional theory calculations, (ii) the feasibility of performing geometry optimisations, (iii) the possibility to model band gaps of insulators and (iv) the ligand-field splitting of Ni-doped MgO. Going beyond the classical restriction of parametrising ab initio model potentials only at the Hartree–Fock level-of-theory, this work additionally address the sensitivity of results to the underlying Hamiltonian used to derive the potentials. The results demonstrate that good agreement with periodic density functional theory calculations can be achieved, geometry optimisations are feasible and accurate band gaps and ligand-field splittings can be computed.</p>}},
author = {{Larsson, Ernst D. and Krośnicki, Marek and Veryazov, Valera}},
issn = {{0301-0104}},
keywords = {{Ab-initio model potential; Band gaps; CASPT2; Ionic solids; Ligand-field splitting}},
language = {{eng}},
month = {{10}},
publisher = {{Elsevier}},
series = {{Chemical Physics}},
title = {{A program system for self-consistent embedded potentials for ionic crystals}},
url = {{http://dx.doi.org/10.1016/j.chemphys.2022.111549}},
doi = {{10.1016/j.chemphys.2022.111549}},
volume = {{562}},
year = {{2022}},
}