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Understanding Density-Driven Errors for Reaction Barrier Heights
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DOI：10.1021/acs.jctc.2c00953.png)
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Abstract
En 中文
Delocalization errors, such as charge-transfer and some self -interaction errors, plague computationally efficient and otherwise accurate density functional approximations (DFAs). Evaluating a semilocal DFA non-self-consistently on the Hartree-Fock (HF) density is often recommended as a computationally inexpensive remedy for delocalization errors. For sophisticated meta-GGAs like SCAN, this approach can achieve remarkable accuracy. This HF-DFT (also known as DFA@HF) is often presumed to work, when it significantly improves over the DFA, because the HF density is more accurate than the self-consistent DFA density in those cases. By applying the metrics of density-corrected density functional theory (DFT), we show that HF-DFT works for barrier heights by making a localizing charge-transfer error or density overcorrection, thereby producing a somewhat reliable cancellation of density-and functional-driven errors for the energy. A quantitative analysis of the charge-transfer errors in a few randomly selected transition states confirms this trend. We do not have the exact functional and electron densities that would be needed to evaluate the exact density-and functional-driven errors for the large BH76 database of barrier heights. Instead, we have identified and employed three fully nonlocal proxy functionals (SCAN 50% global hybrid, range-separated hybrid LC-omega PBE, and SCAN-FLOSIC) and their self-consistent proxy densities. These functionals are chosen because they yield reasonably accurate self-consistent barrier heights and because their self-consistent total energies are nearly piecewise linear in fractional electron number-two important points of similarity to the exact functional. We argue that density-driven errors of the energy in a self-consistent density functional calculation are second order in the density error and that large density-driven errors arise primarily from incorrect electron transfers over length scales larger than the diameter of an atom.
Keywords:
GENERALIZED-GRADIENT-APPROXIMATION
GAUSSIAN-BASIS SETS
ZETA-VALENCE QUALITY
FUNCTIONAL-THEORY
HARTREE-FOCK
EXCHANGE
ATOMS
THERMOCHEMISTRY
ACCURACY
DATABASE
Journal
IF:
5.5
Papers:
1.1W
Citations:
5.4W