jp8b07139_si_053.txt (1.56 kB)
Hybridization and Covalency in the Group 2 and Group 12 Metal Cation/Rare Gas Complexes
Version 2 2022-08-23, 14:15
Version 1 2018-09-17, 14:20
dataset
posted on 2018-08-31, 00:00 authored by William
D. Tuttle, Joe P. Harris, Yu Zheng, W. H. Breckenridge, Timothy G. WrightWe provide a consistent
set of interaction energy curves for the
group 2 (IIA) and group 12 (IIB) metal cation/rare gas complexes,
M+–RG, where M+ = Be+–Ra+ and Zn+–Hg+ and RG = He–Rn.
We report spectroscopic constants derived from these, compare them
with available data, and discuss trends in the values. We gain insight
into the interactions that occur using a range of approaches: reduced
potential energy curves; charge and population analyses; molecular
orbital diagrams and contour plots; and Birge–Sponer plots.
Although sp hybridization occurs in the Be+–RG,
Mg+–RG and group 12 M+–RG complexes,
this appears to be minimal and covalency is the main aspect of the
interaction. However, major sd hybridization occurs in the heavier
group 2 M+–RG systems, which increases their interaction
energies but there is minimal covalency. Examination of Birge–Sponer
plots reveals significant curvature in many cases, which we ascribe
to the changing amounts of hybridization or covalency as a function
of internuclear separation. This suggests why the use of a simple
electrostatics-based model potential to describe the interactions
is inadequate.