Guided ion-beam and theoretical studies of the reaction of Os+ (6D) with O2: Adiabatic and nonadiabatic behavior

The bond energy of ReO+: Guided ion-beam and theoretical studies of the reaction of Re+ (7S) with O2

“…In evaluating these various possibilities, it is important to note that the related Os + + O 2 → OsO + + O reaction also exhibited two distinct endothermic features, 33 presumably for the same intrinsic reasons. In addition, the Ir + + O 2 → IrO + + O reaction shows similar behavior, although more subtly.…”

“…This work reveals the energetics, kinetics, and dynamics of the interaction of the rhenium metal cation with O 2 . In previous studies in our laboratory, GIBMS has been used to systematically study the kinetic energy dependent reactions of O 2 with atomic cations of the first-row, [13][14][15][16][17][18][19][20][21] second-row, 15,16,[22][23][24][25][26][27] and third-row transition metals 16,[28][29][30][31][32][33] and main group metals. [34][35][36] In many cases, analyses of the cross sections for the analogues of reaction (1) have enabled determination of the BDEs of the metal oxide cation, MO + .…”

“…As will be seen below, the kinetic energy dependent cross section for reaction (1) is unusual, exhibiting two endothermic features, which parallels similar behavior recently observed for the neighboring element, Os + reacting with O 2 . 33 The reasons behind this behavior are explored in terms of spin-conservation and adiabatic versus nonadiabatic behavior.…”

Periodic trends in gas‐phase oxidation and hydrogenation reactions of lanthanides and 5d transition metal cations

“…These results are consistent with GIBMS studies of the 3d (Fisher et al, 1990) and 4d (Chen & Armentrout, 1995; Sievers, Chen, & Armentrout, 1996a) TM + (including the much lower reactivity of Mo + ). Comparable GIBMS results for the 5d TM + , Hf + –Au + , reacting with O 2 are collected in Figure 1 (Armentrout, 2013; Armentrout & Li, 2013; Hinton et al, 2009, 2013; Li et al, 2010; Zhang & Armentrout, 2003a). The results are consistent with those of Bohme in all cases.…”

“…Indeed, calculations of the potential energy surfaces for these reactions showed that surfaces of A′ and A″ symmetry are qualitatively different in the entrance channels for all three metals (Armentrout, 2013;Armentrout & Li, 2013;Hinton et al, 2013). For Re + , no low-energy F I G U R E 1 Cross sections for reactions of O 2 with Hf + (red triangles), Ta + (black circles), W + (green inverted triangles) (Hinton et al, 2009), Re + (blue squares) (Armentrout, 2013), Os + (pink diamonds) (Hinton et al, 2013), Ir + (purple triangles) (Armentrout & Li, 2013), Pt + (red inverted triangles) (Zhang & Armentrout, 2003a), Au + ( 1 S) (yellow circles), and Au + ( 3 D) (yellow triangles) (Li et al, 2010) pathways are available along the A′ surfaces, whereas for Os + and Ir + , A″ surfaces have barriers in the entrance channels. At higher kinetic energies, coupling of the A′ and A″ surfaces can occur by electronic-rotational (Coriolis) coupling, as observed for reactions of state-specific rare gas cations (Ar + , Kr + , and Xe + ) with H 2 , D 2 , and HD (Ervin & Armentrout, 1985, 1986a.…”