A method is developed for generating pseudopotentials for use in correlated-electron calculations. The paradigms of shape and energy consistency are combined and defined in terms of correlated-electron wave-functions. The resulting energy consistent correlated electron pseudopotentials (eCEPPs) are constructed for H, Li–F, Sc–Fe, and Cu. Their accuracy is quantified by comparing the relaxed molecular geometries and dissociation energies which they provide with all electron results, with all quantities evaluated using coupled cluster singles, doubles, and triples calculations. Errors inherent in the pseudopotentials are also compared with those arising from a number of approximations commonly used with pseudopotentials. The eCEPPs provide a significant improvement in optimised geometries and dissociation energies for small molecules, with errors for the latter being an order-of-magnitude smaller than for Hartree-Fock-based pseudopotentials available in the literature. Gaussian basis sets are optimised for use with these pseudopotentials.
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28 May 2017
Research Article|
May 25 2017
Shape and energy consistent pseudopotentials for correlated electron systems
J. R. Trail
;
J. R. Trail
a)
Theory of Condensed Matter Group,
Cavendish Laboratory
, J J Thomson Avenue, Cambridge CB3 0HE, United Kingdom
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R. J. Needs
R. J. Needs
Theory of Condensed Matter Group,
Cavendish Laboratory
, J J Thomson Avenue, Cambridge CB3 0HE, United Kingdom
Search for other works by this author on:
J. Chem. Phys. 146, 204107 (2017)
Article history
Received:
March 22 2017
Accepted:
May 11 2017
Citation
J. R. Trail, R. J. Needs; Shape and energy consistent pseudopotentials for correlated electron systems. J. Chem. Phys. 28 May 2017; 146 (20): 204107. https://doi.org/10.1063/1.4984046
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