Electron transfer and bond-forming reactions following collisions of I²⁺with CO and CS₂

Abstract

Collisions between I 2+ and CO have been investigated using time-of flight mass spectrometry at a range of centre-of-mass collision energies between 0.5 eV and 3.0 eV. Following I 2+ + CO collisions we detect I + + CO + from a single-electron transfer reaction and IO + + C + from bond-forming reactivity. Reaction-window calculations, based on Landau-Zener theory, have been used to rationalise the electron transfer reactivity and computational chemistry has been used to explore the [I-CO] 2+ potential energy surface to account for the observation of IO +. In addition, collisions between I 2+ and CS2 have been investigated over a range of centre-of-mass collision energies between 0.8 eV and 6.0 eV. Both single and double electron transfer reactions are observed in the I 2+ /CS2 collision system, an observation again rationalized by reaction-window theory. The monocations IS + and IC + are also detected following collisions of I 2+ with CS2, and these ions are clearly products from a bond-forming reaction. We present a simple model based on the structure of the [I-CS2] 2+ collision complex to rationalize the significantly larger yield of IS + than IC + in this bond-forming process.

Ionisation of PF3: absolute partial electron ionisation cross sections and the formation and reactivity of dication states

“…This methodology has been successfully used in the past, by several groups, to determine dication geometries and energetics. 57 Along with the geometries of an isolated PF 3 2+ ion, the geometries of [Ar-PF 3 ] 2+ complexes were also investigated.…”

Bimolecular reactions of CH2CN2+ with Ar, N2 and CO: reactivity and dynamics

“…The above methodology has been successfully used in previous work to determine the geometries and energetics of dications. 88,99 Readers are referred to the SI for the full geometrical data for each dication structure.…”

“…87 CO has been used as a collision partner in several studies of dication reactivity. 70,84,[88][89][90][91] Collisions between HCl 2+ and CO resulted in PT forming COH + . 89 In the light of these previous studies, we may hypothesise that PT is a likely consequence of CH 2 CN 2+ collisions with neutrals.…”

Bond-forming and electron-transfer reactivity between Ar2+ and N2

“…From the dynamics it is clear that this channel originates from double electron transfer (DET), via the formation of N 2 2+ , as the N + + N + ions are effectively isotropically scattered about the velocity of the N 2 reactant. Such DET reactions are commonly observed in dicationic collision systems, 37,108,109 where two electrons transfer from N 2 to the Ar 2+ ion and the nascent N 2 2+ ion then dissociates. As discussed in more detail in our previous work, 26,37 dicationic DET usually favours a concerted mechanism in which the product and reactant asymptotes lie close in energy (o1 eV).…”