Approaching the Basis Set Limit in Gaussian-Orbital-Based Periodic Calculations with Transferability: Performance of Pure Density Functionals for Simple Semiconductors

Abstract

Simulating solids with quantum chemistry methods and Gaussian-type orbitals (GTOs) has been gaining popularity. Nonetheless, there are few systematic studies that assess the basis set incompleteness error (BSIE) in these GTO-based simulations over a variety of solids. In this work, we report a GTO-based implementation for solids, and apply it to address the basis set convergence issue. We employ a simple strategy to generate large uncontracted (unc) GTO basis sets, that we call the unc-def2-GTH sets. These basis sets exhibit systematic improvement towards the basis set limit as well as good transferability based on application to a total of 43 simple semiconductors. Most notably, we found the BSIE of unc-def2-QZVP-GTH to be smaller than 0.7 mE h per atom in total energies and 20 meV in band gaps for all systems considered here. Using unc-def2-QZVP-GTH, we report band gap benchmarks of a combinatorially designed meta generalized gradient functional (mGGA), B97M-rV, and show that B97M-rV performs similarly (a root-mean-squaredeviation (RMSD) of 1.18 eV) to other modern mGGA functionals, M06-L (1.26 eV), MN15-L (1.29 eV), and SCAN (1.20 eV). This represents a clear improvement over older pure functionals such as LDA (1.71 eV) and PBE (1.49 eV) though all these mGGAs are still far from being quantitatively accurate. We also provide several cautionary notes on the use of our uncontracted bases and on future research on GTO basis set development for solids.

Correlation-consistent Gaussian basis sets for solids made simple

“…These diffuse functions cause significant linear dependencies when used in periodic calculations, [38][39][40][41] leading to numerical instabilities in the self-consistent field (SCF) calculations. 42 While this SCF convergence issue can sometimes be solved by discarding diffuse primitives in the basis set 40 or by canonical orthogonalization, 43 these modifications hinder reproducibility, cause discontinuities in potential energy surfaces, and degrade the quality of virtual orbitals, which affects subsequent correlated calculations. More importantly, the linear dependency problem is worse for larger basis sets, preventing convergence of a periodic calculation to the CBS limit.…”