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

Amou Akhgarnusch; Wai Kit Tang; Han Zhang; Chi-Kit Siu; Martin K. Beyer

doi:10.1039/c6cp03324e

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

Amou Akhgarnusch, Wai Kit Tang, Han Zhang, Chi-Kit Siu^*, Martin K. Beyer^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

24 Citations (Scopus)

34 Downloads (CityUHK Scholars)

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^-, ΔH_hyd(CO₂^-) = -334 ± 44 kJ mol^-1 and ΔH_hyd(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.

Original language	English
Pages (from-to)	23528-23537
Journal	Physical Chemistry Chemical Physics
Volume	18
Issue number	34
Online published	30 Jul 2016
DOIs	https://doi.org/10.1039/c6cp03324e
Publication status	Published - 14 Sept 2016

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

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.",

author = "Amou Akhgarnusch and Tang, {Wai Kit} and Han Zhang and Chi-Kit Siu and Beyer, {Martin K.}",

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

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K

AU - Akhgarnusch, Amou

AU - Tang, Wai Kit

AU - Zhang, Han

AU - Siu, Chi-Kit

AU - Beyer, Martin K.

PY - 2016/9/14

Y1 - 2016/9/14

N2 - 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.

AB - 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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DO - 10.1039/c6cp03324e

M3 - RGC 21 - Publication in refereed journal

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JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

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

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