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Accurate Atomic Correlation and Total Energies for Correlation Consistent Effective Core Potentials
journal contribution
posted on 2020-02-20, 21:30 authored by Abdulgani Annaberdiyev, Cody A. Melton, M. Chandler Bennett, Guangming Wang, Lubos MitasVery 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 elementswithin 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.
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QMC calculationsquantum Monte Carlocore Hamiltonianscorrelation energiesfixed-node diffusion Monte Carlo energiesAccurate Atomic Correlationconfiguration interactionCI calculationsquantum chemistrymany-body approachesfixed-node biasesTotal Energiesfuture use6 basis setsfuture high-accuracy calculationsEffective Core PotentialsCCspace sampling QMCcore potentialsccECPstructure methodsresults offersingle-reference trial wave functionswave function methodsmatter physicsenergy calculations
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