Dear Editor,The electron affinities (EAs) of organic molecules are important properties with experimental values determined by various experimental methods including the measurement of thermal electron attachment in the electron capture detector, ECD, and by negative‐ion mass spectrometry as a function of temperature, electron transfer reactions, photon methods and half‐wave reduction potentials. The uncertainties in these methods have been reported to be of the order of 10–30 meV. In 2015, the newest method from mass spectrometry negative‐ion lifetimes, NILT, was applied to the determination of the EAa of eleven substituted nitrobenzenes. This method depends on calibrations determined by other methods and gives a large difference of 140 meV for the EA of 3,4‐dichloronitrobenzene (1.30 eV) from the literature value of 1.44(5) eV. In this letter, we use the literature electron affinities determined by multiple methods to improve the accuracy of the reported ground state electron affinities. The energy differences between neutrals and anions are: adiabatic electron affinities, EAa, in the most stable geometries; vertical electron affinities, EAv, in the neutral geometries; and photodetachment energies; EApd, in the anion geometries. The ground state adiabatic electron affinity, gs‐EAa, is the energy difference between the neutral and anions in their ground states.The general methods of measuring
Rapid Communications in Mass Spectrometry – Wiley
Published: Jan 15, 2018
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