Evidence for Emergent Chemical Bonding in Au+-Rg Complexes (Rg = Ne, Ar, Kr, and Xe) Export

@article{Breckenridge2008, abstract = {Abstract: Evidence is presented that there is a clear covalent component in the bonding of Au+ to Kr and Au+ to Xe, with some evidence that there may be such bonding between Au+ and Ar; for Au+ and Ne, there is no such evidence, and the bonding seems to be entirely physical. A model potential analysis shows that when all attractive inductive and dispersive terms out to R-8 are properly included in the Au+-Ne case, with an Ae-bR Born-Mayer repulsive term, essentially all the bonding in Au+-Ne can be rationalized by physical attraction alone. This is consistent with a natural bond order (NBO) analysis of the Au+-Ne ab initio wavefunctions, which shows the charge on Au+ to be very close to 1.0. In contrast, similar model potential and NBO analyses show quite clearly that physical interactions alone cannot account for the large bond energy values for the Au+-Kr and Au+-Xe complexes and are consistent with covalent contributions to the Au+-Kr and Au+-Xe interactions. Au+-Ar is seen to lie on the borderline between these two limits. In performing the model potential analyses, high-level ab initio calculations are employed [CCSD(T) energies, extrapolated to the complete basis set limit], to obtain reliable values of Re, De and e as input. A comparison of the gold-Xe bond distances in several solid-state Au(I, II and III) oxidation-state complex ions, containing "ligand" Xe atoms, prepared by Seppelt and co-workers, with that of the "free" Au+-Xe gas-phase ion is made, and a discussion of the trends is presented.}, address = {School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.}, author = {Breckenridge, W. H. and Ayles, V. L. and Wright, T. G.}, citeulike-article-id = {3139571}, citeulike-linkout-0 = {http://dx.doi.org/10.1021/jp711886a}, citeulike-linkout-1 = {http://pubs.acs.org/doi/abs/10.1021/jp711886a}, day = {8}, doi = {10.1021/jp711886a}, journal = {J. Phys. Chem. A}, keywords = {complex, gas, noble}, month = {May}, number = {18}, pages = {4209--4214}, posted-at = {2008-08-20 11:35:42}, priority = {2}, title = {Evidence for Emergent Chemical Bonding in Au+-Rg Complexes (Rg = Ne, Ar, Kr, and Xe)}, url = {http://dx.doi.org/10.1021/jp711886a}, volume = {112}, year = {2008} }

TY - JOUR ID - Breckenridge2008 L3 - citeulike-article-id:3139571 N2 - Abstract: Evidence is presented that there is a clear covalent component in the bonding of Au+ to Kr and Au+ to Xe, with some evidence that there may be such bonding between Au+ and Ar; for Au+ and Ne, there is no such evidence, and the bonding seems to be entirely physical. A model potential analysis shows that when all attractive inductive and dispersive terms out to R-8 are properly included in the Au+-Ne case, with an Ae-bR Born-Mayer repulsive term, essentially all the bonding in Au+-Ne can be rationalized by physical attraction alone. This is consistent with a natural bond order (NBO) analysis of the Au+-Ne ab initio wavefunctions, which shows the charge on Au+ to be very close to 1.0. In contrast, similar model potential and NBO analyses show quite clearly that physical interactions alone cannot account for the large bond energy values for the Au+-Kr and Au+-Xe complexes and are consistent with covalent contributions to the Au+-Kr and Au+-Xe interactions. Au+-Ar is seen to lie on the borderline between these two limits. In performing the model potential analyses, high-level ab initio calculations are employed [CCSD(T) energies, extrapolated to the complete basis set limit], to obtain reliable values of Re, De and e as input. A comparison of the gold-Xe bond distances in several solid-state Au(I, II and III) oxidation-state complex ions, containing "ligand" Xe atoms, prepared by Seppelt and co-workers, with that of the "free" Au+-Xe gas-phase ion is made, and a discussion of the trends is presented. IS - 18 JF - J. Phys. Chem. A AD - School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K. EP - 4214 TI - Evidence for Emergent Chemical Bonding in Au+-Rg Complexes (Rg = Ne, Ar, Kr, and Xe) VL - 112 SP - 4209 KW - complex KW - gas KW - noble AU - Breckenridge, WH AU - Ayles, VL AU - Wright, TG PY - 2008/05/08/ UR - http://dx.doi.org/10.1021/jp711886a ER -