Revisiting the Half-and-Half Functional DOI
Montgomery Gray,

Aniket Mandal,

John M. Herbert

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

Hybrid density functionals typically provide significantly better accuracy than semilocal functionals. Conventional wisdom holds that incorporating more 20-25% exact exchange is deleterious to thermochemical properties and should only be used as a last resort, for problems are dominated by self-interaction error. In such cases, the Becke-Lee-Yang-Parr "half-and-half" functional (BH&H-LYP) has emerged go-to choice, especially in time-dependent theory calculations excitation energies. Here, we examine assumption 50% Hartree-Fock sacrifices accuracy. Using sequence of B(α)LYP, with different percentages (0 ≤ α 100), find BH&H-LYP (with = 50) nearly optimal affords similar B3LYP thermochemistry, barrier heights, Although less accurate atomization energies, this emerges sole rationale taboo against values > 25. Overall, reasonable choice error, including charge-transfer complexes core-level While remains valence use appears an acceptable compromise, can without undue concern over its diminished ground-state properties.

Language: Английский

Revisiting the Half-and-Half Functional DOI
Montgomery Gray,

Aniket Mandal,

John M. Herbert

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

Hybrid density functionals typically provide significantly better accuracy than semilocal functionals. Conventional wisdom holds that incorporating more 20-25% exact exchange is deleterious to thermochemical properties and should only be used as a last resort, for problems are dominated by self-interaction error. In such cases, the Becke-Lee-Yang-Parr "half-and-half" functional (BH&H-LYP) has emerged go-to choice, especially in time-dependent theory calculations excitation energies. Here, we examine assumption 50% Hartree-Fock sacrifices accuracy. Using sequence of B(α)LYP, with different percentages (0 ≤ α 100), find BH&H-LYP (with = 50) nearly optimal affords similar B3LYP thermochemistry, barrier heights, Although less accurate atomization energies, this emerges sole rationale taboo against values > 25. Overall, reasonable choice error, including charge-transfer complexes core-level While remains valence use appears an acceptable compromise, can without undue concern over its diminished ground-state properties.

Language: Английский

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