4484
1991
eng
article
1
2010-12-10
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Pseudopotential Approaches to Ca, Sr and Ba Hybrides. Why are some Alkaline Earth MX\(_2\) Compounds Bent?
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.
urn:nbn:de:bvb:20-opus-31646
3164
The journal of chemical physics (1991) 94, 2, 1360-1366.
Deutsches Urheberrecht
Martin Kaupp
P. v. R. Schleyer
H. Stoll
H. Preuss
deu
swd
Chemie
Chemie und zugeordnete Wissenschaften
open_access
Institut für Anorganische Chemie
Universität Würzburg
https://opus.bibliothek.uni-wuerzburg.de/files/4484/Kaupp_Pseudopotential.pdf