TY  - JOUR
A1  - Kaupp, Martin
A1  - Stoll, H.
A1  - Preuss, H.
T1  - Pseudopotential Calculations for Methyl Compounds of Zinc and Magnesium
N2  - Pseudopotentials and valence basis sets to be used in calculations for organometallic compounds of zinc and magnesium have been tested in calculations for the M(CH\(_3\))\(_n\) (M = Zn, Mg; n = 1,2) molecules. Valence correlation effects are treated at the SDCI and CEPA levels. The capability of a polarization potential on zinc to account for the valence shell contracting effect of core valence correlation is studied. Properties considered are geometries, force constants, Mulliken populations, ionization potentials, atomization, and binding energies. Differences in bonding between the two dimethyl compounds are discussed.
KW  - Zink
KW  - Magnesium
Y1  - 1990
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-46194
ER  - 
TY  - JOUR
A1  - Kaupp, Martin
A1  - Schleyer, P. v. R.
A1  - Stoll, H.
A1  - Preuss, H.
T1  - Pseudopotential Approaches to Ca, Sr and Ba Hybrides. Why are some Alkaline Earth MX\(_2\) Compounds Bent?
N2  - Quasirelativistic and nonrelativistic lo-valence-electronp seudopotentialsf or Ca, Sr, and Ba are presented. Results of calculations with 6s6p5d basis sets for MH, MH\(^+\) , and MH\(_2\), are compared with all-electron and 2-valence-electron pseudopotential calculations with and , without core-polarization potentials. The lo-valence-electron pseudopotential approach agrees well with all-electron calculations. It circumvents problems for the 2-valence-electron pseudopotentials arising from an incomplete separation of valence and subvalence shells in polar molecular systems due to strongly contracted occupied (n - 1 )-d orbitals. All higherlevel calculations show SrH\(_2\) and BaII\(_2\), to be bent with angles of - 140° and 120°, respectively, while CaH\(_2\) is linear with a flat potential-energy surface for the bending motion. The use of a core-polarization potential together with the 2-valence-electronp seudopotentiala pproach allows an investigation of the relative importance of core-polarization vs direct d-orbital bonding participation as reasons for the bent structures. The calculations strongly suggest that both contribute to the bending in SrH\(_2\) and BaII\(_2\). Even at the Hartree-Fock level of theory lovalence- electronp seudopotentialc alculations given reasonablea nglesw hen the potentialenergy surface is not exceedingly flat, and only moderately contracted basis sets including both compact d functions and diffuse p functions are used. The effect of core-valence correlation and the importance off functions also are discussed.
KW  - Chemie
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-31646
ER  -