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.
Wang, Guangming, et al. "A new generation of effective core potentials from correlated and spin–orbit calculations: Selected heavy elements." Journal of Chemical Physics, vol. 157, no. 5, Aug. 2022. https://doi.org/10.1063/5.0087300
Wang, Guangming, Kincaid, Benjamin, Zhou, Haihan, Annaberdiyev, Abdulgani, Bennett, M. Chandler, Krogel, Jaron T., & Mitas, Lubos (2022). A new generation of effective core potentials from correlated and spin–orbit calculations: Selected heavy elements. Journal of Chemical Physics, 157(5). https://doi.org/10.1063/5.0087300
Wang, Guangming, Kincaid, Benjamin, Zhou, Haihan, et al., "A new generation of effective core potentials from correlated and spin–orbit calculations: Selected heavy elements," Journal of Chemical Physics 157, no. 5 (2022), https://doi.org/10.1063/5.0087300
@article{osti_1879560,
author = {Wang, Guangming and Kincaid, Benjamin and Zhou, Haihan and Annaberdiyev, Abdulgani and Bennett, M. Chandler and Krogel, Jaron T. and Mitas, Lubos},
title = {A new generation of effective core potentials from correlated and spin–orbit calculations: Selected heavy elements},
annote = {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.},
doi = {10.1063/5.0087300},
url = {https://www.osti.gov/biblio/1879560},
journal = {Journal of Chemical Physics},
issn = {ISSN 0021-9606},
number = {5},
volume = {157},
place = {United States},
publisher = {American Institute of Physics},
year = {2022},
month = {08}}