Short-range screened density matrix functional for proper descriptions of thermochemistry, thermochemical kinetics, nonbonded interactions, and singlet diradicals

• Published in: The Journal of chemical physics Vol. 159; no. 17
• Main Authors: Ai, Wenna, Su, Neil Qiang, Fang, Wei-Hai
• Format: Journal Article
• Language: English
• Published: Melville American Institute of Physics 07.11.2023
• Subjects: Atomizing; Correlation; Density functional theory; Equilibrium; Kinetics; Physics; Thermochemistry
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/5.0169234

Common one-electron reduced density matrix (1-RDM) functionals that depend on Coulomb and exchange-only integrals tend to underestimate dynamic correlation, preventing reduced density matrix functional theory (RDMFT) from achieving comparable accuracy to density functional theory in main-group thermochemistry and thermochemical kinetics. The recently developed ωP22 functional introduces a semi-local density functional to screen the erroneous short-range portion of 1-RDM functionals without double-counting correlation, potentially providing a better treatment of dynamic correlation around equilibrium geometries. Herein, we systematically evaluate the performance of this functional model, which consists of two parameters, on main-group thermochemistry, thermochemical kinetics, nonbonded interactions, and more. Tests on atomization energies, vibrational frequencies, and reaction barriers reveal that the ωP22 functional model can reliably predict properties at equilibrium and slightly away from equilibrium geometries. In particular, it outperforms commonly used density functionals in the prediction of reaction barriers, nonbonded interactions, and singlet diradicals, thus enhancing the predictive power of RDMFT for routine calculations of thermochemistry and thermochemical kinetics around equilibrium geometries. Further development is needed in the future to refine short- and long-range approximations in the functional model in order to achieve an excellent description of properties both near and far from equilibrium geometries.