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WIREs Comput Mol Sci
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Pseudopotentials and modelpotentials

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Abstract The basic assumptions of quantum chemical ab initio valence‐only (VO) schemes, i.e., pseudopotential and modelpotential approaches, are briefly discussed. Both effective core potential schemes lead to a reduction of the computational effort for wavefunction‐based as well as density functional theory electronic structure calculations in comparison to corresponding all‐electron treatments and allow to include the most important relativistic contributions implicitly into formally nonrelativistic calculations by means of a suitable parameterization of the VO model Hamiltonian. © 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 200‐210 DOI: 10.1002/wcms.28 This article is categorized under: Structure and Mechanism > Molecular Structures Electronic Structure Theory > Ab Initio Electronic Structure Methods

Valence electron systems for Ti small‐core (Ne core) and large‐core (Ar core) pseudopotentials in comparison to the all‐electron treatment. The energetic and spatial separation of core and valence can be judged from the orbital energies ε and radial expectation values <r> (a.u.).

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Errors wrt experimental data in CCSD(T) 1/l3 basis set extrapolated 3dn4s2‐>3dn+14s1, 3dn+2, 3dn4s1, 3dn+1 excitation/ionization energies for DHF/DC + B‐adjusted Ne‐core PPs17 and AE DKH calculations for Sc – Ni. Basis sets: DKH 25s20p15d13f11g9h, PP 15s1515d13f11g9h.

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Pseudo‐valence orbitals for a Ti DHF/DC + B‐adjusted Ne core pseudopotential17 in comparison to relativistic AE DHF/DC orbitals.

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Errors wrt AE data in valence energies of J‐levels for a DHF/DC + B‐adjusted Ne‐core PP for Ti.17

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Errors wrt AE data in valence energies of configurational averages for a DHF/DC + B‐adjusted Ne‐core PP for Ti.17

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Reference data to be used in the adjustment of a Ti small‐core (Ne core) energy‐consistent pseudopotential.17

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Scalar‐relativistic radial potentials Vl of an energy‐consistent17 (solid lines) and a shape‐consistent28 (dashed lines) Ti small‐core (Ne core) pseudopotential. The Ti12+ core electron density (dotted line, arbitrary units) is given for orientation.

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