Relativistic compact effective potentials (RCEP), which replace the atomic core electrons in molecular calculations, have been derived from numerical Dirac–Fock atomic wavefunctions using shape-con...

Relativistic compact effective potentials and efficient, shared-exponent basis sets for the third-, fourth-, and fifth-row atoms

We suggest a new contraction of the basis sets associated with the Hay-Wadt relativistic effective core potentials (RECPs) for the main group and transition metal atoms. These bases are more suitable for density functional theory investigations than the previous ‘double-ζ’ contractions based upon Hartree−Fock atomic results. The original Hay-Wadt primitives are now contracted [5s5p3d], [4s4p3d], and [4s4p3d] for the first, second, and third transition series, respectively, and denoted as LANL2TZ basis sets. For the main group atoms, we advocate using a completely uncontracted basis denoted LANL08. While modestly extending the size of the basis, the resulting sets should be suitable for both DFT and wave function based approaches. The valence bases for the transition metal atoms can be supplemented with the polarization functions determined by Frenking.

Revised Basis Sets for the LANL Effective Core Potentials.

A set of d-polarization functions for pseudo-potential basis sets of the main group elements AlBi and f-type polarization functions for Zn, Cd, Hg

The ternary system consisting of [RuCl2(η6-benzene)]2, N-tosylethylenediamine or ethanolamine, and KOH (Ru:amine:KOH = 1:1:2 molar ratio) catalyzes reversible hydrogen transfer between alcohols and carbonyl compounds. The use of chiral amine auxiliaries effects asymmetric transformation. The theoretical calculations using methanol/formaldehyde transformation as the model indicates the operation of a novel metal−ligand bifunctional catalysis, which is contrary to currently accepted putative pathways. The results reveal that:  (1) KOH is necessary for the generation of a formal 16-electron Ru complex, Ru(NHCH2CH2Y)(η6-benzene) (Y = O or NH) (catalyst), from an 18-electron Ru chloride, RuCl(NH2CH2CH2Y)(η6-benzene) (precatalyst), by a Dcb elimination of HCl, and not for increasing alkoxide concentration; (2) Ru alkoxides do not intervene in transfer hydrogenation; (3) the Ru alkoxide, even if formed, serves merely as a reservoir of the 16-electron catalyst; (4) the key 18-electron Ru hydride, RuH(NH2CH2CH2Y)(...

The Metal−Ligand Bifunctional Catalysis: A Theoretical Study on the Ruthenium(II)-Catalyzed Hydrogen Transfer between Alcohols and Carbonyl Compounds

Diffuse and polarization functions have been optimized for the LANL2DZ basis set for elements in groups 14−17. The optimized exponents are in most cases similar to those optimized with different effective core potentials, valence basis sets, or computational models. The average of the LANL2DZ results for different models is taken to be the best generalized set of exponents. The extended basis set gives good results (average deviation from experiment 0.11 eV) for atomic electron affinities with the B3LYP model, but is consistently low with the MP2 model. The extended basis set gives similar performance to the all-electron 6-31+G(d) basis set in calculations of vibrational frequencies and bond energies in selected main-group compounds, and is intermediate in speed between the 6-31+G(d) basis set and the unmodified LANL2DZ basis set.

Addition of Polarization and Diffuse Functions to the LANL2DZ Basis Set for P-Block Elements

A set of f-polarization functions for pseudo-potential basis sets of the transition metals ScCu, YAg and LaAu

A set of d-polarization functions for pseudo-potential basis sets of the main group elements Al-Bi and f-type polarization functions for Zn, Cd, Hg (Chem. Phys. Letters 208 (1993) 237)

R. Stegmann

Papers

A set of f-polarization functions for pseudo-potential basis sets of the transition metals ScCu, YAg and LaAu

A set of d-polarization functions for pseudo-potential basis sets of the main group elements AlBi and f-type polarization functions for Zn, Cd, Hg

A set of d-polarization functions for pseudo-potential basis sets of the main group elements Al-Bi and f-type polarization functions for Zn, Cd, Hg (Chem. Phys. Letters 208 (1993) 237)