Accurate Atomic Correlation and Total Energies for Correlation Consistent Effective Core Potentials

Abdulgani Annaberdiyev, Cody A. Melton, M. Chandler Bennett, Guangming Wang, Lubos Mitas

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

Very recently, we introduced a set of correlation consistent effective core potentials (ccECPs) constructed within full many-body approaches. By employing significantly more accurate correlated approaches, we were able to reach a new level of accuracy for the resulting effective core Hamiltonians. We also strived for simplicity of use and easy transferability into a variety of electronic structure methods in quantum chemistry and condensed matter physics. Here, as a reference for future use, we present exact or nearly exact total energy calculations for these ccECPs. The calculations cover H-Kr elements and are based on the state-of-the-art configuration interaction (CI), coupled-cluster (CC), and quantum Monte Carlo (QMC) calculations with systematically eliminated/improved errors. In particular, we carry out full CI/CCSD(T)/CCSDT(Q) calculations with cc-pVnZ with up to n = 6 basis sets and we estimate the complete basis set limits. Using combinations of these approaches, we achieved an accuracy of ≈1-10 mHa for K-Zn atoms and ≈0.1-0.3 mHa for all other elements - within about 1% or better of the ccECP total correlation energies. We also estimate the corresponding kinetic energies within the feasible limit of full CI calculations. In order to provide data for QMC calculations, we include fixed-node diffusion Monte Carlo energies for each element that give quantitative insights into the fixed-node biases for single-reference trial wave functions. The results offer a clear benchmark for future high-accuracy calculations in a broad variety of correlated wave function methods such as CI and CC as well is in stochastic approaches such as real space sampling QMC.

Original languageEnglish
Pages (from-to)1482-1502
Number of pages21
JournalJournal of Chemical Theory and Computation
Volume16
Issue number3
DOIs
StatePublished - Mar 10 2020
Externally publishedYes

Funding

We are grateful to Paul R. C. Kent for the reading of the manuscript and helpful suggestions. 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 research used resources of 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. The authors also acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for additional HPC resources. This work describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under Contract DE-NA0003525. We are grateful to Paul R. C. Kent for the reading of the manuscript and helpful suggestions. 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 research used resources of 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. The authors also acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for additional HPC resources. This work describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under Contract DE-NA0003525.

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