Effect of d-orbital occupation on the coordination geometry of metal hydrates: full-gradient ab initio calculations on metal ion monohydrates Academic Article uri icon


  • Hartree-Fock-Roothaan self-consistent-field calculations were performed on monohydrates of the metal ions Li+, Na+, K+, Ca2+, Sc3+, Ti2+, Cr2+, Co+, and Ni2+ and the neutral Fe0. Optimal geometries were calculated with the requirement that Cs symmetry be maintained. From these calculations the effect of the electronic interaction on the metal-water coordination geometry was isolated from bulk effects and its strength estimated. Potential energy curves were calculated for the metal ion versus the angle θW (the “wag angle”). The potential energy curve for this wagging motion was found to be shallow, and in all cases except Fe0 the planar, C2v, geometry (θW = 0°) was found to have the lowest energy. The potential curve depended strongly on the charge of the ion and weakly on the d-orbital occupation of the transition metals. © 1988, American Chemical Society. All rights reserved.

author list (cited authors)

  • Davy, R. D., & Hall, M. B.

citation count

  • 10

publication date

  • April 1988