ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img
RETURN TO ISSUEPREVA: New Tools and Met...A: New Tools and Methods in Experiment and TheoryNEXT

Implementation and Validation of Local Hybrid Functionals with Calibrated Exchange-Energy Densities for Nuclear Shielding Constants

  • Caspar Jonas Schattenberg
    Caspar Jonas Schattenberg
    Theoretische Chemie/Quantenchemie, Institut für Chemie, Technische Universität Berlin, Sekr. C7, Straße des 17. Juni 135, D-10623 Berlin, Germany
  •  and 
  • Martin Kaupp*
    Martin Kaupp
    Theoretische Chemie/Quantenchemie, Institut für Chemie, Technische Universität Berlin, Sekr. C7, Straße des 17. Juni 135, D-10623 Berlin, Germany
    *Email: [email protected]
    More by Martin Kaupp
Cite this: J. Phys. Chem. A 2021, 125, 12, 2697–2707
Publication Date (Web):March 18, 2021
https://doi.org/10.1021/acs.jpca.1c01135
Copyright © 2021 The Authors. Published by American Chemical Society

    Article Views

    309

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    A recently reported coupled-perturbed Kohn–Sham implementation to compute nuclear shielding constants with gauge-including atomic orbitals and local hybrid functionals has been extended to cover higher derivatives of the density in the local mixing function (LMF) of the local hybrid as well as the calibration function (CF) needed to deal with the ambiguity of exchange-energy densities. This allowed the first evaluation of state-of-the-art local hybrids with “calibrated” exchange-energy densities for nuclear shieldings. Compared to previously evaluated simpler local hybrids without a CF, appreciable improvements are found for proton shieldings. Furthermore, the recent LH20t functional is still competitive with the outstanding performance of the uncalibrated LH12ct-SsirSVWN and LH12ct-SsifSVWN LHs for heavier nuclei, suggesting that LH20t is possibly the most robust choice of any rung-four functional for computing the nuclear shieldings of main-group nuclei so far. Interestingly, the presence of a CF in the functional significantly reduces the number of artifacts introduced by the widely used Maximoff–Scuseria framework to treat the local kinetic energy τ. The latter occurs in so-called t-LMFs used in many of the present local hybrids. In any case, the use of Dobson’s current-density functional framework is also recommended with more advanced calibrated τ-dependent local hybrid functionals.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.1c01135.

    • Tables with additional shielding results and statistics and figures with statistical distributions (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 13 publications.

    1. Caspar Jonas Schattenberg, Martin Kaupp. Implementation and First Evaluation of Strong-Correlation-Corrected Local Hybrid Functionals for the Calculation of NMR Shieldings and Shifts. The Journal of Physical Chemistry A 2024, 128 (11) , 2253-2271. https://doi.org/10.1021/acs.jpca.3c08507
    2. Caspar J. Schattenberg, Artur Wodyński, Hugo Åström, Dage Sundholm, Martin Kaupp, Susi Lehtola. Revisiting Gauge-Independent Kinetic Energy Densities in Meta-GGAs and Local Hybrid Calculations of Magnetizabilities. The Journal of Physical Chemistry A 2023, 127 (51) , 10896-10907. https://doi.org/10.1021/acs.jpca.3c06244
    3. Van Anh Tran, Markus Teucher, Laura Galazzo, Bikramjit Sharma, Tim Pongratz, Stefan M. Kast, Dominik Marx, Enrica Bordignon, Alexander Schnegg, Frank Neese. Dissecting the Molecular Origin of g-Tensor Heterogeneity and Strain in Nitroxide Radicals in Water: Electron Paramagnetic Resonance Experiment versus Theory. The Journal of Physical Chemistry A 2023, 127 (31) , 6447-6466. https://doi.org/10.1021/acs.jpca.3c02879
    4. T. Trepl, I. Schelter, S. Kümmel. Analyzing Excitation-Energy Transfer Based on the Time-Dependent Density Functional Theory in Real Time. Journal of Chemical Theory and Computation 2022, 18 (11) , 6577-6587. https://doi.org/10.1021/acs.jctc.2c00600
    5. Artur Wodyński, Martin Kaupp. Local Hybrid Functional Applicable to Weakly and Strongly Correlated Systems. Journal of Chemical Theory and Computation 2022, 18 (10) , 6111-6123. https://doi.org/10.1021/acs.jctc.2c00795
    6. Caspar Jonas Schattenberg, Morten Lehmann, Michael Bühl, Martin Kaupp. Systematic Evaluation of Modern Density Functional Methods for the Computation of NMR Shifts of 3d Transition-Metal Nuclei. Journal of Chemical Theory and Computation 2022, 18 (1) , 273-292. https://doi.org/10.1021/acs.jctc.1c00964
    7. Caspar Jonas Schattenberg, Martin Kaupp. Extended Benchmark Set of Main-Group Nuclear Shielding Constants and NMR Chemical Shifts and Its Use to Evaluate Modern DFT Methods. Journal of Chemical Theory and Computation 2021, 17 (12) , 7602-7621. https://doi.org/10.1021/acs.jctc.1c00919
    8. Sebastian Gillhuber, Yannick J. Franzke, Florian Weigend. Paramagnetic NMR Shielding Tensors and Ring Currents: Efficient Implementation and Application to Heavy Element Compounds. The Journal of Physical Chemistry A 2021, 125 (44) , 9707-9723. https://doi.org/10.1021/acs.jpca.1c07793
    9. Andrew M. Teale, Trygve Helgaker, Andreas Savin, Carlo Adamo, Bálint Aradi, Alexei V. Arbuznikov, Paul W. Ayers, Evert Jan Baerends, Vincenzo Barone, Patrizia Calaminici, Eric Cancès, Emily A. Carter, Pratim Kumar Chattaraj, Henry Chermette, Ilaria Ciofini, T. Daniel Crawford, Frank De Proft, John F. Dobson, Claudia Draxl, Thomas Frauenheim, Emmanuel Fromager, Patricio Fuentealba, Laura Gagliardi, Giulia Galli, Jiali Gao, Paul Geerlings, Nikitas Gidopoulos, Peter M. W. Gill, Paola Gori-Giorgi, Andreas Görling, Tim Gould, Stefan Grimme, Oleg Gritsenko, Hans Jørgen Aagaard Jensen, Erin R. Johnson, Robert O. Jones, Martin Kaupp, Andreas M. Köster, Leeor Kronik, Anna I. Krylov, Simen Kvaal, Andre Laestadius, Mel Levy, Mathieu Lewin, Shubin Liu, Pierre-François Loos, Neepa T. Maitra, Frank Neese, John P. Perdew, Katarzyna Pernal, Pascal Pernot, Piotr Piecuch, Elisa Rebolini, Lucia Reining, Pina Romaniello, Adrienn Ruzsinszky, Dennis R. Salahub, Matthias Scheffler, Peter Schwerdtfeger, Viktor N. Staroverov, Jianwei Sun, Erik Tellgren, David J. Tozer, Samuel B. Trickey, Carsten A. Ullrich, Alberto Vela, Giovanni Vignale, Tomasz A. Wesolowski, Xin Xu, Weitao Yang. DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science. Physical Chemistry Chemical Physics 2022, 24 (47) , 28700-28781. https://doi.org/10.1039/D2CP02827A
    10. Martin Kaupp, Caspar J. Schattenberg, Robert Müller, Marc Reimann. Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19 F NMR Shifts versus Thermochemistry. ChemistryOpen 2022, 11 (12) https://doi.org/10.1002/open.202200146
    11. Christof Holzer, Yannick J. Franzke. A local hybrid exchange functional approximation from first principles. The Journal of Chemical Physics 2022, 157 (3) https://doi.org/10.1063/5.0100439
    12. Yannick J. Franzke, Christof Holzer. Impact of the current density on paramagnetic NMR properties. The Journal of Chemical Physics 2022, 157 (3) https://doi.org/10.1063/5.0103898
    13. Robin Grotjahn, Martin Kaupp. Assessment of hybrid functionals for singlet and triplet excitations: Why do some local hybrid functionals perform so well for triplet excitation energies?. The Journal of Chemical Physics 2021, 155 (12) https://doi.org/10.1063/5.0063751

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect