Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals

1985/01/01 by P. Jeffrey Hay, Willard R. Wadt · 15,517 citations
Chemistry · Materials Science · Physics and Astronomy · #Ab initio #Advanced Chemical Physics Studies #Atomic orbital #Atomic physics #Chemistry #Core (optical fiber) #Core electron #Crystallography and molecular interactions #Electron #Molecular orbital #Molecular orbital theory #Molecular physics #Molecule #Physics #Quantum mechanics #Row #Valence (chemistry) #X-ray Diffraction in Crystallography

paper · doi:10.1063/1.448975

published in The Journal of Chemical Physics 82(1), 299-310 (American Institute of Physics)

openalex publication_date 1985/01/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

Ab initio effective core potentials (ECP’s) have been generated to replace the innermost core electron for third-row (K–Au), fourth-row (Rb–Ag), and fifth-row (Cs–Au) atoms. The outermost core orbitals—corresponding to the ns2np6 configuration for the three rows here—are not replaced by the ECP but are treated on an equal footing with the nd, (n+1)s and (n+1)p valence orbitals. These ECP’s have been derived for use in molecular calculations where these outer core orbitals need to be treated explicitly rather than to be replaced by an ECP. The ECP’s for the forth and fifth rows also incorporate the mass–velocity and Darwin relativistic effects into the potentials. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3s, 3p, 3d, 4s, 4p), (4s, 4p, 4d, 5s, 5p), and (5s, 5p, 5d, 6s, 6p) ortibals of the three respective rows.

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