Relative stability of isomers of polynuclear complexes of molybdenum oxides

• Published in: Russian journal of inorganic chemistry 2010, Vol.55 (12), p.1919-1929
• Main Authors: Norov, Yu. V, Parshakov, A. S, Yarzhemskii, V. G, Il'in, E. G, Buryak, A. K
• Format: Article
• Language: English
• Subjects: Bond energy; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Ionization; Isomers; Mathematical analysis; Molybdenum oxides; Oxides; Quantum chemistry; Stability; Theoretical Inorganic Chemistry
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023610120168

Molybdenum(VI) oxide MoO₃ has been studied and the composition of polynuclear molybdenum oxides in the gas phase Mo x O₃x − y (x = 1-6, y = 0-2) has been determined by laser desorption/ionization time-of-flight mass spectrometry. Quantum-chemical calculations of bond energies, interatomic distances, charge distributions, and molybdenum-molybdenum bond orders for the isomers of neutral polynuclear molecular compounds Mo x O3 x − y have been performed with the use of the PBE functional with a relativistically corrected potential implemented as the PRIRODA program package. On the basis of the bond energies, the relative stability of the isomers has been estimated. For the Mo x O y isomers (x ≥ 3), cyclic structures have been predicted to be more favorable. For the predicted most stable isomers of each Mo x O y composition, the bond energies of their positive and negative ions have been calculated. The positive ionization of Mo x O y leads to a considerable decrease in the bond energy of the isomer and the negative ionization, to its increase by about 0.1 au.