Addition of a Hydrogen Atom to Acetonitrile by Hydrated Electrons in Nanodroplets

Abstract

Nanodroplets that contain hydrated electrons provide information complementary to standard radiolysis techniques. Although the reaction of hydrated electrons with acetonitrile was observed in solution 25 years ago, its product has only now been identified in a gas‐phase experiment as the hydrogen adduct. The picture shows a solvent‐stabilized radical anion, which is suggested as a reactive intermediate.

Free electrons, the simplest radicals of them all: chemistry of aqueous electrons as studied by mass spectrometry

“…The clusters or "nandodroplets" thus provide a suitable medium, free of interference by impurities, where the lifetime of the free electrons is not limited by the presence of protons. This then permits convenient studies of the chemistry of these interesting reactants, as already exemplified by a series of investigations both in our laboratory [23,39,40] and earlier by Johnson and coworkers [41,42]. These studies of hydrated electron reactions and chemistry form the subject of the present review.…”

“…Haberland and coworkers have demonstrated, that gas phase hydrated electrons, that is small negatively charged water clusters (H 2 O) n − can be produced [15][16][17], and since then these species have been quite extensively studied, both experimentally [18][19][20][21][22][23] and theoretically [24][25][26][27][28][29][30][31][32][33][34]. A more extensive account of these works is given in a previous publication [21].…”

“…One can also first produce neutral water clusters in a supersonic expansion, and subsequently attach low energy electrons [35][36][37]. Quite recently we have demonstrated, that a versatile laser vaporization source developed in our laboratory can be used as a very efficient, clean source of hydrated electrons [21,23]. This source which combines supersonic expansion with pulsed laser vaporization of a solid metal sample can generate metal cations and cationic clusters, as well as electrons, anions and anionic clusters.…”

“…This source which combines supersonic expansion with pulsed laser vaporization of a solid metal sample can generate metal cations and cationic clusters, as well as electrons, anions and anionic clusters. When one employs a metal sample with negative electron affinity, such as zinc, the metal anions and anion clusters can effectively be eliminated [23]. When a small amount of water vapor is then introduced into the high pressure carrier gas, usually helium, pure hydrated electron clusters are produced.…”

Ion–molecule reactions of CoAr6+ with nitrogen oxides N2O, NO, and NO2: measuring absolute pressure by shock-freezing of the collision complex

“…Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is a well suited tool to investigate bimolecular cluster ion-molecule reactions [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. In order to determine absolute rate constants one should know the absolute pressure in the ICR-cell accurately, because the pressure is the main uncertainty.…”