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.

arXiv comment49 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]

References in corpus (30)

• Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections
• Long-range/short-range separation of the electron-electron interaction in density functional theory
• The radical character of the acenes: A density matrix renormalization group study
• A well-tempered density functional theory of electrons in molecules
• Distribution of occupation numbers in finite Fermi-systems and role of interaction in chaos and thermalization
• Fractional spins and static correlation error in density functional theory
• Electronic Ground State of Higher Acenes
• Describing static correlation in bond dissociation by Kohn-Sham density functional theory
• Double-hybrid density-functional theory made rigorous
• SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters
• Statistical Theory of Finite Fermi-Systems Based on the Structure of Chaotic Eigenstates
• Density functional theory with fractional orbital occupations
• Seeking for reliable double-hybrid density functionals without fitting parameters: The PBE0-2 functional
• Time-dependent density functional study of the electronic spectra of oligoacenes in the charge states -1, 0, +1, and +2
• Long-range corrected hybrid meta-generalized-gradient approximations with dispersion corrections
• Exchange-Correlation Energy from Pairing Matrix Fluctuation and the Particle-Particle Random Phase Approximation
• Rationale for a new class of double-hybrid approximations in density-functional theory
• Towards a Statistical Theory of Finite Systems and Compound States: Random Two-Body Interaction Approach
• Thermally-assisted-occupation density functional theory with generalized-gradient approximations
• Role of Kekulé and Non-Kekulé Structures in the Radical Character of Alternant Polycyclic Aromatic Hydrocarbons: A TAO-DFT Study
• Electronic Properties of Cyclacenes from TAO-DFT
• Equivalence of Particle-Particle Random Phase Approximation Correlation Energy and Ladder-Coupled-Cluster-Double
• Structural and Electronic Instabilities in Polyacenes: Density Matrix Renormalization Group Study of a Long--Range Interacting Model
• Assessment of Density Functional Methods for Exciton Binding Energies and Related Optoelectronic Properties
• Effect of Li Adsorption on the Electronic and Hydrogen Storage Properties of Acenes: A Dispersion-Corrected TAO-DFT Study
• Assessment of density functional methods with correct asymptotic behavior
• Double-hybrid density-functional theory with meta-generalized-gradient approximations
• Short- and long-range corrected hybrid density functionals with the D3 dispersion corrections
• Temperature-Dependent Behavior of Confined Many-electron Systems in the Hartree-Fock Approximation
• Van der Waals interactions in rare-gas dimers: The role of interparticle interactions

Cited by in corpus (9)

• Fully numerical calculations on atoms with fractional occupations. Range-separated exchange functionals
• Effect of Li Termination on the Electronic and Hydrogen Storage Properties of Linear Carbon Chains: A TAO-DFT Study
• Fate of the open-shell singlet ground state in the experimentally accessible acenes: a quantum Monte Carlo study
• 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
• Static Correlation Density Functional Theory
• Spin Symmetry in Thermally-Assisted-Occupation Density Functional Theory
• Approximate density matrix functionals applied to hetero-atomic bond dissociation
• Finite-Temperature Thermally-Assisted-Occupation Density Functional Theory, Ab Initio Molecular Dynamics, and Quantum Mechanics/Molecular Mechanics Methods