Double-Hybrid DFT Functionals for the Condensed Phase: Gaussian and Plane Waves Implementation and Evaluation

• Published in: Molecules (Basel, Switzerland) Vol. 25; no. 21; p. 5174
• Main Authors: Stein, Frederick, Hutter, Jürg, Rybkin, Vladimir V
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 06.11.2020; MDPI
• Subjects: Accuracy; Ammonia - chemistry; Approximation; benchmark, wave-function correlation method; Catalysis; Cell size; Crystal structure; Crystallization; Density Functional Theory; double-hybrid functionals; Energy; Hydrogen Cyanide - chemistry; Integrals; Methods; Models, Chemical; Models, Molecular; Normal Distribution; Plane waves; double-hybrid functionals; benchmark, wave-function correlation method; density functional theory
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules25215174

Intermolecular interactions play an important role for the understanding of catalysis, biochemistry and pharmacy. Double-hybrid density functionals (DHDFs) combine the proper treatment of short-range interactions of common density functionals with the correct description of long-range interactions of wave-function correlation methods. Up to now, there are only a few benchmark studies available examining the performance of DHDFs in condensed phase. We studied the performance of a small but diverse selection of DHDFs implemented within Gaussian and plane waves formalism on cohesive energies of four representative dispersion interaction dominated crystal structures. We found that the PWRB95 and ωB97X-2 functionals provide an excellent description of long-ranged interactions in solids. In addition, we identified numerical issues due to the extreme grid dependence of the underlying density functional for PWRB95. The basis set superposition error (BSSE) and convergence with respect to the super cell size are discussed for two different large basis sets.