Range-separated double-hybrid density-functional theory applied to periodic systems

TL;DR

This paper develops and tests a range-separated double-hybrid density functional theory for periodic systems, demonstrating good accuracy in predicting binding energies across various crystal types using moderate basis sets.

Contribution

It introduces a new implementation of range-separated double hybrids for periodic systems and benchmarks their performance, including the use of spin-component-scaled MP2.

Findings

Range-separation parameter μ=0.5 bohr^{-1} is suitable for solids.

Range-separated double hybrids achieve good accuracy with moderate basis sets.

Spin-component-scaled MP2 improves long-range correlation treatment.

Abstract

Quantum chemistry methods exploiting density-functional approximations for short-range electron-electron interactions and second-order M{{\o}}ller-Plesset (MP2) perturbation theory for long-range electron-electron interactions have been implemented for periodic systems using Gaussian-type basis functions and the local correlation framework. The performance of these range-separated double hybrids has been benchmarked on a significant set of systems including rare-gas, molecular, ionic, and covalent crystals. The use of spin-component-scaled MP2 for the long-range part has been tested as well. The results show that the value of $\mu$ = 0.5 bohr^{--1} for the range-separation parameter usually used for molecular systems is also a reasonable choice for solids. Overall, these range-separated double hybrids provide a good accuracy for binding energies using basis sets of moderate sizes such as cc-pVDZ and aug-cc-pVDZ.