Methane Adducts of Gold Dimer Cations: Thermochemistry and Structure from Collision-Induced Dissociation and...

The bond dissociation energies at 0 K (BDE) of Au₂⁺-CH₄ and Au₂CH₄⁺-CH₄ have been determined using two separate experimental methods. Analyses of collision-induced dissociation cross sections for Au₂CH₄⁺ + Xe and Au₂(CH₄)₂⁺ + Xe measured using a guided ion beam tandem mass spectrometer (GIBMS) yield BDEs of 0.71 ± 0.05 and 0.57 ± 0.07 eV, respectively. Statistical modeling of association kinetics of Au₂(CH₄)_0-2⁺ + CH₄ + He measured from 200 to 400 K and at 0.3-0.9 Torr using a selected-ion flow tube (SIFT) apparatus yields slightly higher values of 0.81 ± 0.21 and 0.75 ± 0.25 eV. The SIFT data also place a lower limit on the BDE of Au₂C₂H₈⁺-CH₄ of 0.35 eV, likely an activated isomer, not Au₂(CH₄)₂⁺-CH₄. Particular emphasis is placed on determining the uncertainty in the derivation from association kinetics measurements, including uncertainties in collisional energy transfer, calculated harmonic frequencies, and possible contribution of isomerization of the association complexes. This evaluation indicates that an uncertainty of ±0.2 eV should be expected and that an uncertainty of better than ±0.1 eV is unlikely to be reasonable.