Role of exact exchange in thermally-assisted-occupation density functional theory: A proposal of new hybrid schemes

Abstract

We propose hybrid schemes incorporating exact exchange into thermally-assisted-occupation density functional theory (TAO-DFT) [J.-D. Chai, J. Chem. Phys. 136, 154104 (2012)] for an improved description of nonlocal exchange effects. With a few simple modifications, global and range-separated hybrid functionals in Kohn-Sham density functional theory (KS-DFT) can be combined seamlessly with TAO-DFT. In comparison with global hybrid functionals in KS-DFT, the resulting global hybrid functionals in TAO-DFT yield promising performance for systems with strong static correlation effects (e.g., the dissociation of H2 and N2, twisted ethylene, and electronic properties of linear acenes), while maintaining similar performance for systems without strong static correlation effects. Besides, a reasonably accurate description of noncovalent interactions can be efficiently achieved through the inclusion of dispersion corrections in hybrid TAO-DFT. Relative to semilocal density functionals in TAO-DFT, global hybrid functionals in TAO-DFT are generally superior in performance for a wide range of applications, such as thermochemistry, kinetics, reaction energies, and optimized geometries.

49 pages, 17 figures, 4 tables, supplementary material not included. This is an extension of our previous works [e.g., see arXiv:1201.4866, arXiv:1401.0380]

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Cited by in corpus (4)

• Excitation Energies from Thermally-Assisted-Occupation Density Functional Theory: Theory and Computational Implementation
• Combining density based dynamical correlation with a reduced density matrix strong correlation description
• Spin Symmetry in Thermally-Assisted-Occupation Density Functional Theory
• Finite-Temperature Thermally-Assisted-Occupation Density Functional Theory, Ab Initio Molecular Dynamics, and Quantum Mechanics/Molecular Mechanics Methods