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Basis-set correction based on density-functional theory: Linear-response formalism for excited-state energies.
- Source :
-
The Journal of chemical physics [J Chem Phys] 2023 Jun 21; Vol. 158 (23). - Publication Year :
- 2023
-
Abstract
- The basis-set correction method based on density-functional theory consists in correcting the energy calculated by a wave-function method with a given basis set by a density functional. This basis-set correction density functional incorporates the short-range electron correlation effects missing in the basis set. This results in accelerated basis convergences of ground-state energies to the complete-basis-set limit. In this work, we extend the basis-set correction method to a linear-response formalism for calculating excited-state energies. We give the general linear-response equations as well as the more specific equations for configuration-interaction wave functions. As a proof of concept, we apply this approach to the calculations of excited-state energies in a one-dimensional two-electron model system with harmonic potential and a Dirac-delta electron-electron interaction. The results obtained with full-configuration-interaction wave functions expanded in a basis of Hermite functions and a local-density-approximation basis-set correction functional show that the present approach does not help in accelerating the basis convergence of excitation energies. However, we show that it significantly accelerates basis convergences of excited-state total energies.<br /> (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)
Details
- Language :
- English
- ISSN :
- 1089-7690
- Volume :
- 158
- Issue :
- 23
- Database :
- MEDLINE
- Journal :
- The Journal of chemical physics
- Publication Type :
- Academic Journal
- Accession number :
- 37338026
- Full Text :
- https://doi.org/10.1063/5.0156317