Systematically convergent basis sets with relativistic pseudopotentials. II. Small-core pseudopotentials and correlation consistent basis sets for the post-<i>d</i> group 16–18 elements
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- Kirk A. Peterson
- Department of Chemistry, Washington State University, Pullman, Washington 99164-4630
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- Detlev Figgen
- Institut für Theoretische Chemie, Universität Stuttgart, D-70550 Stuttgart, Germany
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- Erich Goll
- Institut für Theoretische Chemie, Universität Stuttgart, D-70550 Stuttgart, Germany
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- Hermann Stoll
- Institut für Theoretische Chemie, Universität Stuttgart, D-70550 Stuttgart, Germany
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- Michael Dolg
- Institut für Theoretische Chemie, Universität zu Köln, D-50939 Köln, Germany
説明
<jats:p>A series of correlation consistent basis sets have been developed for the post-d group 16–18 elements in conjunction with small-core relativistic pseudopotentials of the energy-consistent variety. The latter were adjusted to multiconfiguration Dirac–Hartree–Fock data based on the Dirac–Coulomb–Breit Hamiltonian. The outer-core (n−1)spd shells are explicitly treated together with the nsp valence shell with these PPs. The accompanying cc-pVnZ-PP and aug-cc-pVnZ-PP basis sets range in size from DZ to 5Z quality and yield systematic convergence of both Hartree–Fock and correlated total energies. In addition to the calculation of atomic electron affinities and dipole polarizabilities of the rare gas atoms, numerous molecular benchmark calculations (HBr, HI, HAt, Br2, I2, At2, SiSe, SiTe, SiPo, KrH+, XeH+, and RnH+) are also reported at the coupled cluster level of theory. For the purposes of comparison, all-electron calculations using the Douglas–Kroll–Hess Hamiltonian have also been carried out for the halogen-containing molecules using basis sets of 5Z quality.</jats:p>
収録刊行物
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- The Journal of Chemical Physics
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The Journal of Chemical Physics 119 (21), 11113-11123, 2003-12-01
AIP Publishing