Cobalt, rhodium, and iridium dioxide molecules and Walsh-type rules

A Critical Appraisal of the Experimental Data on the Molecular Structure and Spectra of Halides, Oxides, and Hydrides of the s-, d-, and f-Block Elements

“…[97] It is noteworthy that in the case of molybdenum, with seven isotopes of natural abundance greater than 9 %, it was possible to use 16 (symmetrical) 16 O 2 or 18 O 2 species to calculate an upper limit to the angle (1258), and more than 40 isotopomers to calculate a lower limit (1198). RuO 2 was reported [98] to have a bond angle of 1498, and if RhO 2 and IrO 2 are linear, as indicated by ESR measurements, [99] then the general pattern for the second-and third-row transition element dioxides appears to be similar to that established for the first row.…”

Transition-metal dioxides: A case for the intersite term in Hubbard-model functionals

“…A large number of experimental studies of inserted dioxides have been carried out on the mid-row transitionmetal dioxides, MnO 2 , [9][10][11] FeO 2 , [12][13][14] and CoO 2 . [15][16][17][18] Experimentally, the early-to mid-row transition-metal dioxides prefer bent structures, while the later transition-metal oxides have linear structures. The mid-row transition-metal oxides represent a formidable challenge for theoretical calculations, which, while extensive for MnO 2 , 19,20 FeO 2 ,8,[20][21][22] and CoO 2 , 20,23,24 have been inconclusive or contradictory with respect to experiment.…”

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO3)2 (M = Co, Ni) into Metal–Oxo Species

“…[28,29] The assignment of CoO 2 rather than Co + O 2 or CoO + O as the neutral product of Reaction (9) is based on ab initio studies of this system, which predict the dioxide CoO 2 as the energetically preferred species. [30,31] [(H 2 O)Co(NO 3 (9) Whereas Reaction (4) is a mere ligand loss from the hydrated monocation, Reaction (5) + as a function of collision energy; note that the secondary fragments are summed into the primary fragments. [32] Loss of a water ligand requires an appearance energy of AE(4) = (1.7 Ϯ 0.2) eV, a value which is right in the ballpark of water binding energies for bare or singly ligated metal cations, [20,27,33,34] lending confidence to the method for the approximate determination of appearance energies applied here.…”