Abstract
We introduce new correlation consistent effective core potentials (ccECPs) for the elements I, Te, Bi, Ag, Au, Pd, Ir, Mo, and W with 4d, 5d, 6s, and 6p valence spaces. These ccECPs are given as a sum of spin-orbit averaged relativistic effective potential (AREP) and effective spin-orbit (SO) terms. The construction involves several steps with increasing refinements from more simple to fully correlated methods. The optimizations are carried out with objective functions that include weighted many-body atomic spectra, norm-conservation criteria, and SO splittings. Transferability tests involve molecular binding curves of corresponding hydride and oxide dimers. The constructed ccECPs are systematically better and in a few cases on par with previous effective core potential (ECP) tables on all tested criteria and provide a significant increase in accuracy for valence-only calculations with these elements. Our study confirms the importance of the AREP part in determining the overall quality of the ECP even in the presence of sizable spin-orbit effects. The subsequent quantum Monte Carlo calculations point out the importance of accurate trial wave functions that, in some cases (mid-series transition elements), require treatment well beyond a single-reference.
| Original language | English |
|---|---|
| Article number | 054101 |
| Journal | Journal of Chemical Physics |
| Volume | 157 |
| Issue number | 5 |
| DOIs | |
| State | Published - Aug 7 2022 |
Funding
This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, as part of the Computational Materials Sciences Program and Center for Predictive Simulation of Functional Materials. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). This research used resources from the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. This research used resources from the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract No. DE-AC02-06CH11357. This research also used resources from the Oak Ridge Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract No. DE-AC05-00OR22725.