A seminumerical algorithm capable of performing large-scale (time-dependent) density functional theory (TD-DFT) calculations to extract excitation energies and other ground-state and excited-state properties is outlined. The algorithm uses seminumerical integral techniques for evaluating Coulomb and exchange parts for a set of density matrices as occurring in standard TD-DFT or similar methods for the evaluation of vibrational frequencies. A suitable optimized de-aliasing procedure is introduced. The latter does not depend on further auxiliary quantities and retains the symmetry of a given density matrix. The algorithm is self-contained and applicable to any orbital basis set available without the need for further auxiliary basis sets or optimized de-aliasing grids. Relativistic two-component excited-state TD-DFT calculations are reported for the first time using the developed seminumerical algorithm for standard and local hybrid density functional approximations. Errors are compared with the widely used “resolution of the identity” (RI) approximations for Coulomb (RI-J) and exchange integrals (RI-K). The fully seminumerical algorithm does not exhibit an enlarged error for standard DFT functionals compared to the RI approximation. For the more involved local hybrid functionals and within strong external fields, accuracy is even considerably improved.
Skip Nav Destination
Article navigation
14 November 2020
Research Article|
November 12 2020
An improved seminumerical Coulomb and exchange algorithm for properties and excited states in modern density functional theory
Christof Holzer
Christof Holzer
a)
Institute of Theoretical Solid State Physics, Karlsruhe Institute of Technology (KIT)
, Wolfgang-Gaede-Straße 1, 76131 Karlsruhe, Germany
a)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
Christof Holzer
a)
Institute of Theoretical Solid State Physics, Karlsruhe Institute of Technology (KIT)
, Wolfgang-Gaede-Straße 1, 76131 Karlsruhe, Germany
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 153, 184115 (2020)
Article history
Received:
July 23 2020
Accepted:
October 27 2020
Citation
Christof Holzer; An improved seminumerical Coulomb and exchange algorithm for properties and excited states in modern density functional theory. J. Chem. Phys. 14 November 2020; 153 (18): 184115. https://doi.org/10.1063/5.0022755
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Assessment of hybrid functionals for singlet and triplet excitations: Why do some local hybrid functionals perform so well for triplet excitation energies?
J. Chem. Phys. (September 2021)
Importance of imposing gauge invariance in time-dependent density functional theory calculations with meta-generalized gradient approximations
J. Chem. Phys. (September 2022)
A local hybrid exchange functional approximation from first principles
J. Chem. Phys. (July 2022)
Relativistic local hybrid functionals and their impact on 1s core orbital energies
J. Chem. Phys. (June 2020)