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Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons.

ABSTRACT: The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

SUBMITTER: Lengyel J

PROVIDER: S-EPMC7116334 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

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Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons.

Lengyel Jozef J Med Jakub J Slavíček Petr P Beyer Martin K MK

The Journal of chemical physics 20170901 10

The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO ...[more]

PMID: 28915744

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