Empirical Double-Hybrid Density Functional Theory: A 'Third Way' In Between WFT and DFT

TL;DR

This paper discusses the development and performance of empirical double hybrid density functional theory, which offers a promising balance between wavefunction methods and DFT, achieving high accuracy with relatively low computational cost.

Contribution

It introduces empirical double hybrid functionals with dispersion corrections that approach wavefunction accuracy at a computational cost similar to hybrid DFT, requiring few parameters.

Findings

Achieves near wavefunction accuracy for large benchmarks

Provides intermediate vibrational frequency accuracy between CCSD and CCSD(T)

Performs well for organometallic reactions with limited static correlation

Abstract

Double hybrid density functional theory arguably sits on the seamline between wavefunction methods and DFT: it represents a special case of Rung 5 on the "Jacobs Ladder" of John P. Perdew. For large and chemically diverse benchmarks such as GMTKN55, empirical double hybrid functionals with dispersion corrections can achieve accuracies approaching wavefunction methods at a cost not greatly dissimilar to hybrid DFT approaches, provided RI-MP2 and/or another MP2 acceleration techniques are available in the electronic structure code. Only a half-dozen or fewer empirical parameters are required. For vibrational frequencies, accuracies intermediate between CCSD and CCSD(T) can be achieved, and performance for other properties is encouraging as well. Organometallic reactions can likewise be treated well, provided static correlation is not too strong. Further prospects are discussed, including range-separated and RPA-based approaches.