Previous studies demonstrated the suitability of density functional theory (DFT) for calculating the core-valence correlation energya. The new PFD-3B functionalb has now been applied to calculating scalar relativistic corrections. These corrections are calculated using Douglas-Kroll-Hess (DKH) second-order perturbation theory, as the difference between DKH relativistic calculations with DKH optimized basis sets, compared to the analogous non-relativistic calculations with non-relativistic optimized basis sets.We compared the results of the calculated scalar relativistic energy corrections for the first-row transition metals and their diatomic molecules using PFD-3B DFT with a 3ZaPa, triple z basis set vs. coupled cluster theory, CCSD(T), in the complete basis set (CBS) limit. The mean absolute deviation of the PFD-3B/3ZaPa values with respect to the CCSD(T)/CBS values is only 0.11 kcal/mol. These accurate results in addition to the low computational cost of PFD-3B DFT show that DFT is a viable method for calculating scalar relativistic effects.

Inexpensive Kohn-Sham density functional method for scalar and spin-orbit relativistic corrections on H–Kr

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.