Empirical Double‐Hybrid Density Functional Theory: A ‘Third Way’ in Between WFT and DFT

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 “Jacob's Ladder” of John P. Perdew. For large and chemically diverse benchmarks such as GMTKN55, empirical double hybrid functionals with dis...

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Bibliographic Details
Published in:	Israel journal of chemistry 2020-08, Vol.60 (8-9), p.787-804
Main Authors:	Martin, Jan M. L., Santra, Golokesh
Format:	Article
Language:	eng
Subjects:	Acceleration Benchmarks Density functional theory Dispersion Double hybrid DFT Electronic structure Empiricity Jacob's Ladder Wave functions
Online Access:	Request full text
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Summary:	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 “Jacob's 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.
ISSN:	0021-2148 1869-5868