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Title: The Good, the Bad, and the Ugly: Pseudopotential Inconsistency Errors in Molecular Applications of Density Functional Theory

Journal Article · · Journal of Chemical Theory and Computation

The pseudopotential (PP) approximation is one of the most common techniques in computational chemistry. Despite its long history, the development of custom PPs has not tracked with the explosion of different density functional approximations (DFAs). As a result, the use of PPs with exchange/correlation models for which they were not developed is widespread, although this practice is known to be theoretically unsound. The extent of PP inconsistency errors (PPIEs) associated with this practice has not been systematically explored across the types of energy differences commonly evaluated in chemical applications. Here, we evaluate PPIEs for a number of PPs and DFAs across 196 chemically relevant systems of both transition-metal and main-group elements, as represented by the W4-11, TMC34, and S22 data sets. Near the complete basis set limit, these PPs are found to cleanly approach all-electron (AE) results for noncovalent interactions but introduce root-mean-squared errors (RMSEs) upwards of 15 kcal mol–1 into predictions of covalent bond energies for a number of popular DFAs. We achieve significant improvements through the use of empirical atom- and DFA-specific PP corrections, indicating considerable systematicity of the PPIEs. The results of this work have implications for chemical modeling in both molecular contexts and for DFA design, which we discuss.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
2294059
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 10 Vol. 19; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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