Density functional with full exact exchange, balanced nonlocality of correlation, and constraint satisfaction

TL;DR

This paper introduces a new nonlocal density functional approximation that combines full exact exchange with balanced correlation, improving accuracy for molecular energies and reaction barriers by interpolating between different density regimes.

Contribution

It presents a size-consistent, fourth-rung hyper-GGA functional with full exact exchange, employing a novel interpolation scheme for different electron density regions.

Findings

Achieves high accuracy for molecular enthalpies and reaction barriers.

Ensures exactness for all one-electron densities.

Provides a balanced treatment of nonlocal exchange and correlation.

Abstract

We construct a nonlocal density functional approximation with full exact exchange, while preserving the constraint-satisfaction approach and justified error cancellations of simpler semilocal functionals. This is achieved by interpolating between different approximations suitable for two extreme regions of the electron density. "Normal" regions are well described by semilocal approximations, because of proper accuracy for a slowly-varying density or because of error cancellation between exchange and correlation. "Abnormal" regions, where nonlocality is unveiled, include those in which exchange can dominate correlation (one-electron, nonuniform high-density, and rapidly-varying limits), and those open subsystems of fluctuating electron number over which the exact exchange-correlation hole integrates to a value greater than -1. Regions between these extremes are described by a hybrid functional mixing exact and semilocal exchange energy densities locally. Because our mixing fraction tends to 1 in the high-density limit, we rigorously employ full exact exchange. However, the nonlocality of exchange also requires balanced nonlocality of correlation, which can demand at least five empirical parameters. Our local hybrid functional is perhaps the first size-consistent fourth-rung density functional or hyper-GGA with full exact exchange, is exact for all one-electron densities, and provides an excellent fit to the 223 molecular enthalpies of formation of the G3/99 set and the 42 reaction barrier heights of the BH42/03 set, improving both (but especially the latter) over most semilocal functionals and global hybrids.