We propose compact and efficient valence-function sets for s- and p-block elements from Li to Rn to appropriately describe valence correlation in model core potential (MCP) calculations. The basis sets are generated by a combination of split MCP valence orbitals and correlating contracted Gaussian-type functions in a segmented form. We provide three types of basis sets. They are referred to as MCP-dzp, MCP-tzp, and MCP-qzp, since they have the quality comparable with all-electron correlation consistent basis sets, cc-pVDZ, cc-pVTZ, and cc-pVQZ, respectively, for lighter atoms. MCP calculations with the present basis sets give atomic correlation energies in good agreement with all-electron calculations. The present MCP basis sets systematically improve physical properties in atomic and molecular systems in a series of MCP-dzp, MCP-tzp, and MCP-qzp. Ionization potentials and electron affinities of halogen atoms as well as molecular spectroscopic constants calculated by the best MCP set are in good agreement with experimental values.

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Contracted Gaussian-type function (CGTF) sets for the description of the 4f subshell correlation and of the 6s and 5d subshell correlation are developed for lanthanide atoms from Ce to Yb. Also prepared are basis sets for the 5d orbitals, which are vacant in the ground states of most lanthanide atoms but are essential in molecular environments. In addition, correlating CGTF sets for the 4f subshell correlation are supplemented for the Lu atom. A segmented contraction scheme is employed for their compactness and efficiency. Contraction coefficients and exponents are determined by minimizing the deviation from accurate natural orbitals generated from configuration interaction calculations that include relativistic effects through the third-order Douglas-Kroll approximation. All-electron and model core potential calculations with the present correlating sets are performed on the ground state of the diatomic CeO molecule. The calculated spectroscopic constants are in good agreement with experimental values.

Contracted Gaussian-type function sets are proposed for polarization functions of the atoms Ga±Kr and In±Xe. We also report polarization functions for Ca and Sr. A segmented contraction scheme is used for its compactness and computational eciency. The contraction coecients and orbital exponents are fully optimized to minimize the deviation from accurate atomic natural orbitals. The present polarization functions yield more than 99% of atomic correlation energies predicted by accurate natural orbitals of the same size. Atomic polarization functionsAs in the previous work [1, 2, 3], both the contraction coecients and the exponents of the GTFs were Correspondence to: M. Sekiya

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