Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Abstract

Reactions of the third-row transition metal cation Os(+) with H(2), D(2), and HD to form OsH(+) (OsD(+)) were studied using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Os(+) in its (6)D (6s(1)5d(6)) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of OsH(+) and OsD(+) are analyzed to give a 0 K bond dissociation energy of D(0)(Os(+)-H) = 2.45 ± 0.10 eV. Quantum chemical calculations are performed here at several levels of theory, with B3LYP approaches generally overestimating the experimental bond energy whereas results obtained using BHLYP and CCSD(T), coupled-cluster with single, double, and perturbative triple excitations, levels show good agreement. Theory also provides the electronic structures of these species and the potential energy surfaces for reaction. Results from the reactions with HD provide insight into the reaction mechanism and indicate that Os(+) reacts via a direct reaction. We also compare this third-row transition metal system with the first-row and second-row congeners, Fe(+) and Ru(+), and find that Os(+) reacts more efficiently with dihydrogen, forming a stronger M(+)-H bond. These differences can be attributed to the lanthanide contraction and relativistic effects.

Activation of CH4 by Th+ as Studied by Guided Ion Beam Mass Spectrometry and Quantum Chemistry

“…22,23,25,27,28,30,53,69,70,86 In all cases, the difference is attributed to competition with the formation of the metal carbene because of a shared, common intermediate. Because reactions of M + with H 2 produce only one product, no competition exists that may delay the onset of reaction.…”

Global diabatic potential energy surfaces for the BeH2+ system and dynamics studies on the Be+(2P) + H2(X1Σg+) → BeH+(X1Σ+) + H(2S) reaction

“…11 On the other hand, the reactive collisions between metal ions and molecular hydrogen (M + + H 2 ) are important objects to study reaction dynamics, and a broad range of M + ions have been performed by the guide ion beam methods in combination with theoretical calculations. [12][13][14][15] The BeH 2 + system has been widely studied in the related elds of cold and ultracold chemistry. In 2006, Roth et al 2 studied the Be + ( 2 P) + H 2 / BeH + + H reaction by a laser-cooling ion trap apparatus with the millikelvin level translational temperatures of Be + ions.…”

Generation of free hydrogen atoms in thermal reaction of ethane with AuNbO 3 + cluster cations

“…Tel. : +86 10 62568330; fax: +86 10 62559373. to the reactivity of bare noble-metal atoms or related cluster species, such as Pt + [21,22], Au 2 + [23], PtAu + [24], Pd 2 + [25], and so on [26][27][28][29][30][31]. These studies have demonstrated rich structure-property relationships in bond activation of small organic and inorganic molecules by noble metals.…”