Fully numerical Hartree-Fock and density functional calculations. I. Atoms

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Lehtola , S 2019 , ' Fully numerical Hartree-Fock and density functional calculations. I. Atoms ' , International Journal of Quantum Chemistry , vol. 119 , no. 19 , 25945 . https://doi.org/10.1002/qua.25945

Title: Fully numerical Hartree-Fock and density functional calculations. I. Atoms
Author: Lehtola, Susi
Contributor organization: Department
Staff Services
Date: 2019-10-05
Language: eng
Number of pages: 30
Belongs to series: International Journal of Quantum Chemistry
ISSN: 0020-7608
DOI: https://doi.org/10.1002/qua.25945
URI: http://hdl.handle.net/10138/311128
Abstract: Although many programs have been published for fully numerical Hartree-Fock (HF) or density functional (DF) calculations on atoms, we are not aware of any programs that support hybrid DFs, which are popular within the quantum chemistry community due to their better accuracy for many applications, or that can be used to calculate electric properties. Here, we present a variational atomic finite element solver in the HelFEM program suite that overcomes these limitations. A basis set of the type chi nlm(r,theta,phi) = r(-1) Bn (r) Upsilon(m)(1) ((r) over cap is used, where B-n(r) are finite element shape functions and Upsilon(m)(1) are spherical harmonics, which allows for an arbitrary level of accuracy. HelFEM supports nonrelativistic HF and DF calculations even with hybrid functionals, which are not available in other commonly available program packages. Hundreds of functionals at the local spin-density approximation (LDA), generalized-gradient approximation (GGA), as well as the meta-GGA levels of theory are included through an interface with the Libxc library. Electric response properties are achievable via finite field calculations. We introduce an alternative grid that yields faster convergence to the complete basis set limit than commonly used alternatives. We also show that high-order Lagrange interpolating polynomials yield the best convergence, and that excellent agreement with literature HF limit values for electric properties, such as static dipole polarizabilities, can be achieved with the present approach. Dipole moments and dipole polarizabilities at finite field are also reported with the PBE, PBEh, TPSS, and TPSSh functionals. Finally, we show that a recently published Gaussian basis set is able to reproduce absolute HF and DF energies of neutral atoms, cations, as well as anions within a few dozen microhartrees.
Description: 44 pages, 11 figures. Small reorganization of intro
atomic calculation
density functional theory
finite element
116 Chemical sciences
114 Physical sciences
Peer reviewed: Yes
Rights: cc_by
Usage restriction: openAccess
Self-archived version: acceptedVersion

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