GW100: A Slater-Type Orbital Perspective

Overview

Journal J Chem Theory Comput

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2021 Jul 8

PMID 34236172

Citations 8

Authors

Arno Forster

Lucas Visscher

Affiliations

Soon will be listed here.

Abstract

We calculate complete basis set (CBS) limit-extrapolated ionization potentials (IPs) and electron affinities (EA) with Slater-type basis sets for the molecules in the GW100 database. To this end, we present two new Slater-type orbital (STO) basis sets of triple-(TZ) and quadruple-ζ (QZ) quality, whose polarization is adequate for correlated-electron methods and which contain extra diffuse functions to be able to correctly calculate EAs of molecules with a positive lowest unoccupied molecular orbital (LUMO). We demonstrate that going from TZ to QZ quality consistently reduces the basis set error of our computed IPs and EAs, and we conclude that a good estimate of these quantities at the CBS limit can be obtained by extrapolation. With mean absolute deviations (MAD) from 70 to 85 meV, our CBS limit-extrapolated IP are in good agreement with results from FHI-AIMS, TURBOMOLE, VASP, and WEST, while they differ by more than 130 meV on average from nanoGW. With a MAD of 160 meV, our EA are also in good agreement with the WEST code. Especially for systems with positive LUMOs, the agreement is excellent. With respect to other codes, the STO-type basis sets generally underestimate EAs of small molecules with strongly bound LUMOs. With 62 meV for IPs and 93 meV for EAs, we find much better agreement with CBS limit-extrapolated results from FHI-AIMS for a set of 250 medium to large organic molecules.

Citing Articles

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References

van Lenthe E, Baerends E . Optimized Slater-type basis sets for the elements 1-118. J Comput Chem. 2003; 24(9):1142-56. DOI: 10.1002/jcc.10255. View

Kresse , Hafner . Ab initio molecular dynamics for liquid metals. Phys Rev B Condens Matter. 1993; 47(1):558-561. DOI: 10.1103/physrevb.47.558. View

Bruneval F . Optimized virtual orbital subspace for faster GW calculations in localized basis. J Chem Phys. 2016; 145(23):234110. DOI: 10.1063/1.4972003. View

Knight J, Wang X, Gallandi L, Dolgounitcheva O, Ren X, Ortiz J . Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules III: A Benchmark of GW Methods. J Chem Theory Comput. 2016; 12(2):615-26. DOI: 10.1021/acs.jctc.5b00871. View

van Setten M, Weigend F, Evers F . The GW-Method for Quantum Chemistry Applications: Theory and Implementation. J Chem Theory Comput. 2015; 9(1):232-46. DOI: 10.1021/ct300648t. View

Stuke A, Kunkel C, Golze D, Todorovic M, Margraf J, Reuter K . Atomic structures and orbital energies of 61,489 crystal-forming organic molecules. Sci Data. 2020; 7(1):58. PMC: 7029047. DOI: 10.1038/s41597-020-0385-y. View

Jacquemin D, Duchemin I, Blase X . Benchmarking the Bethe-Salpeter Formalism on a Standard Organic Molecular Set. J Chem Theory Comput. 2015; 11(7):3290-304. PMC: 4504186. DOI: 10.1021/acs.jctc.5b00304. View

Watson M, Handy N, Cohen A, Helgaker T . Density-functional generalized-gradient and hybrid calculations of electromagnetic properties using Slater basis sets. J Chem Phys. 2004; 120(16):7252-61. DOI: 10.1063/1.1668633. View

Lange M, Berkelbach T . On the Relation between Equation-of-Motion Coupled-Cluster Theory and the GW Approximation. J Chem Theory Comput. 2018; 14(8):4224-4236. DOI: 10.1021/acs.jctc.8b00455. View

10.

Maggio E, Liu P, van Setten M, Kresse G . GW100: A Plane Wave Perspective for Small Molecules. J Chem Theory Comput. 2017; 13(2):635-648. DOI: 10.1021/acs.jctc.6b01150. View

11.

Takatsuka A, Ten-No S, Hackbusch W . Minimax approximation for the decomposition of energy denominators in Laplace-transformed Møller-Plesset perturbation theories. J Chem Phys. 2008; 129(4):044112. DOI: 10.1063/1.2958921. View

12.

Gao W, Chelikowsky J . Real-Space Based Benchmark of GW Calculations on GW100: Effects of Semicore Orbitals and Orbital Reordering. J Chem Theory Comput. 2019; 15(10):5299-5307. DOI: 10.1021/acs.jctc.9b00520. View

13.

Kraus P . Basis Set Extrapolations for Density Functional Theory. J Chem Theory Comput. 2020; 16(9):5712-5722. DOI: 10.1021/acs.jctc.0c00684. View

14.

Duchemin I, Blase X . Cubic-Scaling All-Electron Calculations with a Separable Density-Fitting Space-Time Approach. J Chem Theory Comput. 2021; 17(4):2383-2393. DOI: 10.1021/acs.jctc.1c00101. View

15.

Forster A, Visscher L . Low-Order Scaling by Pair Atomic Density Fitting. J Chem Theory Comput. 2020; 16(12):7381-7399. PMC: 7726916. DOI: 10.1021/acs.jctc.0c00693. View

16.

Riemelmoser S, Kaltak M, Kresse G . Plane wave basis set correction methods for RPA correlation energies. J Chem Phys. 2020; 152(13):134103. DOI: 10.1063/5.0002246. View

17.

Balasubramani S, Chen G, Coriani S, Diedenhofen M, Frank M, Franzke Y . TURBOMOLE: Modular program suite for ab initio quantum-chemical and condensed-matter simulations. J Chem Phys. 2020; 152(18):184107. PMC: 7228783. DOI: 10.1063/5.0004635. View

18.

Kaltak M, Klimes J, Kresse G . Low Scaling Algorithms for the Random Phase Approximation: Imaginary Time and Laplace Transformations. J Chem Theory Comput. 2015; 10(6):2498-507. DOI: 10.1021/ct5001268. View

19.

Maximoff S, Ernzerhof M, Scuseria G . Current-dependent extension of the Perdew-Burke-Ernzerhof exchange-correlation functional. J Chem Phys. 2004; 120(5):2105-9. DOI: 10.1063/1.1634553. View

20.

Golze D, Dvorak M, Rinke P . The Compendium: A Practical Guide to Theoretical Photoemission Spectroscopy. Front Chem. 2019; 7:377. PMC: 6633269. DOI: 10.3389/fchem.2019.00377. View