Multiple bonds to gold: a theoretical investigation of XAuC (X = F, Cl, Br, I) molecules

Structures and spectroscopic properties are reported for the linear XAuC (X = F, Cl, Br, I) series of molecules and their related diatomic species at a high level of accuracy. The singles and doubles coupled cluster method including a perturbational correction for connected triple excitations, CCSD(T), with systematic sequences of new correlation consistent basis sets have been employed, Scalar relativistic effects have been accurately included by making use of relativistic effective core potentials. Extrapolation to the complete basis set limit has been used with accurate treatments of core-valence correlation and spin-orbit effects in order to accurately predict spectroscopic properties, as well as dissociation and atomization energies at 0 K of AuC, AuC+, AuF, AuCl, AuBr, AuI, and the XAuC molecules. The Au-C bond length in the FAuC molecule is predicted to be nearly identical to that calculated for AuC+, which makes it the shortest known for a neutral gold molecule. The Au-C and Au-F (0 K) bond dissociation energies in FAuC are predicted to be 92.5 and 93.1 kcal/mol, respectively, also making them some of the strongest known bonds to gold. (C) 2004 Elsevier B.V. All rights reserved.