title: The antimony-group 11 chemical bond: dissociation energies of the diatomic molecules CuSb, AgSb, and AuSb.
abstract: The intermetallic molecules CuSb, AgSb, and AuSb were identified in the effusive molecular beam produced at high temperature under equilibrium conditions in a double-cell-like Knudsen source. Several gaseous equilibria involving these species were studied by mass spectrometry as a function of temperature in the overall range 1349-1822 K, and the strength of the chemical bond formed between antimony and the group 11 metals was for the first time measured deriving the following thermochemical dissociation energies (D°(0), kJ/mol): 186.7 ± 5.1 (CuSb), 156.3 ± 4.9 (AgSb), 241.3 ± 5.8 (AuSb). The three species were also investigated computationally at the coupled cluster level with single, double, and noniterative quasiperturbative triple excitations (CCSD(T)). The spectroscopic parameters were calculated from the potential energy curves and the dissociation energies were evaluated at the Complete Basis Set limit, resulting in an overall good agreement with experimental values. An approximate evaluation of the spin-orbit effect was also performed. CCSD(T) calculations were further extended to the corresponding group 11 arsenide species which are here studied for the first time and the following dissociation energies (D°(0), kJ/mol): 190 ± 10 (CuAs), 151 ± 10 (AgAs), 240 ± 15 (AuAs) are proposed. Taking advantage of the new experimental and computational information here presented, the bond energy trends along group 11 and 4th and 5th periods of the periodic table were analyzed and the bond energies of the diatomic species CuBi and AuBi, yet experimentally unobserved, were predicted on an empirical basis.
authors: Dipartimento di Chimica, Sapienza Università di Roma, p.le A. Moro 5, 00185 Roma, Italy.
authors: V
authors: V
authors: Carta
authors: Dipartimento di Chimica, Sapienza Università di Roma, p.le A. Moro 5, 00185 Roma, Italy.
authors: A
authors: A
authors: Ciccioli
authors: Dipartimento di Chimica, Sapienza Università di Roma, p.le A. Moro 5, 00185 Roma, Italy.
authors: G
authors: G
authors: Gigli