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

TL;DR

This paper develops a systematic Gaussian basis set approach for solids, demonstrating reduced basis set errors and benchmarking functional performance on semiconductors, advancing quantum chemistry simulations of materials.

Contribution

Introduces a transferability-focused uncontracted GTO basis set for solids and benchmarks its effectiveness in reducing basis set errors and evaluating functional accuracy.

Findings

Basis set incompleteness error less than 0.7 m$E_h$ per atom with the new basis sets.

B97M-rV functional performs comparably to other modern mGGAs in band gap predictions.

Uncontracted basis sets improve convergence but require careful application.

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 m$E_h$ 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-square-deviation (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.