Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Original languageEnglish
Pages (from-to)23528-23537
Journal / PublicationPhysical Chemistry Chemical Physics
Volume18
Issue number34
Online published30 Jul 2016
Publication statusPublished - 14 Sep 2016

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Abstract

The recombination reactions of gas-phase hydrated electrons (H2O)n- with CO2 and O2, as well as the charge exchange reaction of CO2-(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions. Converted to room temperature condensed phase, this yields hydration enthalpies of CO2- and O2-, ΔHhyd(CO2-) = -334 ± 44 kJ mol-1 and ΔHhyd(O2-) = -404 ± 28 kJ mol-1. Quantum chemical calculations show that the charge exchange reaction proceeds via a CO4- intermediate, which is consistent with a fully ergodic reaction and also with the small efficiency. Ab initio molecular dynamics simulations corroborate this picture and indicate that the CO4- intermediate has a lifetime significantly above the ps regime.

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Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K. / Akhgarnusch, Amou; Tang, Wai Kit; Zhang, Han; Siu, Chi-Kit; Beyer, Martin K.

In: Physical Chemistry Chemical Physics, Vol. 18, No. 34, 14.09.2016, p. 23528-23537.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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