Reactions of Large Water Cluster Anions with Hydrogen Chloride:  Formation of Atomic Hydrogen and Phase Separation in the Gas Phase

• Published in: Journal of the American Chemical Society 2007-03, Vol.129 (11), p.3238-3246
• Main Authors: Siu, Chi-Kit, Balaj, O. Petru, Bondybey, Vladimir E, Beyer, Martin K
• Format: Article
• Language: English
• Subjects: Chemical Sciences; or physical chemistry; Theoretical and
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja067355o

The reactions of water cluster anions (H2O) n -, n = 30−70, with hydrogen chloride have been studied by Fourier transform ion cyclotron resonance (FT−ICR) mass spectrometry. The first HCl taken up by the clusters is presumably ionically dissolved. The solvated electron recombines with the proton, which is thereby reduced to atomic hydrogen and evaporates from the cluster. This process is accompanied by blackbody radiation and collision induced loss of water molecules. Subsequent collisions lead to uptake of HCl and loss of H2O, yielding mixed clusters Cl-(HCl) m (H2O) n until they are saturated with HCl. Those saturated clusters lose H2O and HCl in a characteristic sequence. The final stage of the reaction, involving clusters with m = 0−4 and n = 0−6, is studied in detail with density functional theory calculations. The Cl-(HCl)4(H2O)6 cluster represents an example for supramolecular self-organization in the gas phase:  it consists of a tetrahedral Cl-(HCl)4, connected on one side of the tetrahedron to a compact water hexamer.