Hyperfine coupling constants of the nitrogen and phosphorus atoms: A challenge for exact-exchange density-functional and post-Hartree-Fock methods
Kaupp M, Arbuznikov AV, Heßelmann A, Görling A (2010)
Publication Type: Journal article, Original article
Publication year: 2010
Journal
Original Authors: Kaupp M., Arbuznikov A.V., Heßelmann A., Görling A.
Publisher: American Institute of Physics (AIP)
Book Volume: 132
Article Number: 184107
Journal Issue: 18
DOI: 10.1063/1.3417985
Abstract
The isotropic hyperfine coupling constants of the free N (S4) and P (S4) atoms have been evaluated with high-level post-Hartree-Fock and density-functional methods. The phosphorus hyperfine coupling presents a significant challenge to both types of methods. With large basis sets, MP2 and coupled-cluster singles and doubles calculations give much too small values for the phosphorus atom. Triple excitations are needed in coupled-cluster calculations to achieve reasonable agreement with experiment. None of the standard density functionals reproduce even the correct sign of this hyperfine coupling. Similarly, the computed hyperfine couplings depend crucially on the self-consistent treatment in exact-exchange density-functional theory within the optimized effective potential (OEP) method. Well-balanced auxiliary and orbital basis sets are needed for basis-expansion exact-exchange-only OEP approaches to come close to Hartree-Fock or numerical OEP data. Results from the localized Hartree-Fock and Krieger-Li-Iafrate approximations deviate notably from exact OEP data in spite of very similar total energies. Of the functionals tested, only full exact-exchange methods augmented by a correlation functional gave at least the correct sign of the P (S4) hyperfine coupling but with too low absolute values. The subtle interplay between the spin-polarization contributions of the different core shells has been analyzed, and the influence of even very small changes in the exchange-correlation potential could be identified. © 2010 American Institute of Physics.
Authors with CRIS profile
Andreas Heßelmann
Lehrstuhl für Theoretische Chemie
Andreas Görling
Lehrstuhl für Theoretische Chemie
Additional Organisation(s)
Involved external institutions
Germany (DE)How to cite
APA:
Kaupp, M., Arbuznikov, A.V., Heßelmann, A., & Görling, A. (2010). Hyperfine coupling constants of the nitrogen and phosphorus atoms: A challenge for exact-exchange density-functional and post-Hartree-Fock methods. Journal of Chemical Physics, 132(18). https://doi.org/10.1063/1.3417985
MLA:
Kaupp, Martin, et al. "Hyperfine coupling constants of the nitrogen and phosphorus atoms: A challenge for exact-exchange density-functional and post-Hartree-Fock methods." Journal of Chemical Physics 132.18 (2010).
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