Toward the Next Generation of Density Functionals: Escaping the Zero-Sum Game by Using the Exact-Exchange Energy Density

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(13), P. 1815 - 1826

Published: June 21, 2024

ConspectusKohn–Sham density functional theory (KS DFT) is arguably the most widely applied electronic-structure method with tens of thousands publications each year in a wide variety fields. Its importance and usefulness can thus hardly be overstated. The central quantity that determines accuracy KS DFT calculations exchange-correlation functional. exact form unknown, or better "unknowable", therefore derivation ever more accurate yet efficiently applicable approximate functionals "holy grail" field. In this context, simultaneous minimization so-called delocalization errors static correlation greatest challenge needs to overcome as we move toward computationally efficient methods. many cases, an improvement on one these two aspects (also often termed fractional-charge fractional-spin errors, respectively) generates deterioration other one. Here report recent notable progress escaping "zero-sum-game" by constructing new based exact-exchange energy density. particular, local hybrid range-separated are discussed incorporate additional terms deal well errors. Taking hints from coordinate-space models nondynamical strong electron correlations (the B13 KP16/B13 models), position-dependent functions cover real space have been devised incorporated into local-mixing determining position-dependence admixture hybrids treatment range separation hybrids. While initial followed closely frameworks, meanwhile simpler real-space ratios semilocal densities found, providing basis for relatively simple numerically convenient functionals. Notably, correction either increase decrease locally (and interelectronic-distance space), leading even regions negative cases particularly correlations. Efficient implementations fast computer code (Turbomole) using seminumerical integration techniques make such promising tools complicated composite systems research areas, where simultaneously small crucial. First real-world application examples provided, including stretched bonds, symmetry-breaking hyperfine coupling open-shell transition-metal complexes, reduction computation nuclear shieldings magnetizabilities. newest versions (e.g., ωLH23tdE) retain excellent frontier-orbital energies correct asymptotic potential underlying ωLH22t while improving substantially strong-correlation cases. further linked performance impactful deep-neural-network "black-box" DM21, which itself may viewed hybrid.

Language: Английский

Unlocking enhanced photocatalytic potential in copper oxide via Ti, Zn, and Fe based ternary copper (I) oxide: a density functional theory approach

Emergent Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 5, 2024

Language: Английский