Experimental and computational investigation of the group 11-group 2 diatomic molecules: first determination of the AuSr and AuBa bond energies and thermodynamic stability of the copper- and silver-alkaline earth species.

The dissociation energies of the intermetallic molecules AuSr and AuBa were for the first time determined by the Knudsen effusion mass spectrometry method. The two species were produced in the vapor phase equilibrated with apt mixtures of the constituent elements, and the dissociation equilibria were monitored mass-spectrometrically in the temperature range 1406-1971 K (AuSr) and 1505-1971 K (AuBa). The third-law analysis of the equilibrium data gives the following dissociation energies (D(0)°, in kJ/mol): 244.4 ± 4.8 (AuSr) and 273.3 ± 6.3 (AuBa), so completing the series of D(0)°s for the AuAE (AE = group 2 element) diatomics. The AuAE species were also studied computationally at the coupled cluster including single, double and perturbative triple excitation [CCSD(T)] level with basis sets of increasing zeta quality, and various complete basis set limit extrapolations were performed to calculate the dissociation energies. Furthermore, the entire series of the heteronuclear diatomic species formed from one group 11 (Cu, Ag) and one group 2 (Be, Mg, Ca, Sr, Ba) metal was studied by DFT with the hybrid meta-GGA TPSSh functional and the def2-QZVPP basis set, selected after screening a number of functional-basis set combinations using the AuAE species as benchmark. Dissociation energies, internuclear distances, vibrational frequencies, and anharmonic constants were determined for the CuAE and AgAE species and their thermal functions evaluated therefrom. On this basis, a thermodynamic evaluation of the formation of these species was carried out under various conditions.