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Bonding energetics in clusters formed by cesium salts: a study by collision‐induced dissociation and density functional theory
Author(s) -
Maria PierreCharles,
Massi Lionel,
Box Natzaret Sindreu,
Gal JeanFrançois,
Burk Peeter,
TammikuTaul Jaana,
Kutsar Martin
Publication year - 2006
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2552
Subject(s) - chemistry , malonate , dissociation (chemistry) , density functional theory , inorganic chemistry , caesium , ion , hydrogen , oxalate , adduct , hydrogen bond , molecule , computational chemistry , organic chemistry
In relation to the interaction between 137 Cs and soil organic matter, electrospray mass spectrometry experiments and density functional theory (DFT) calculations were carried out on the dissociation of positively charged adducts formed by cesium nitrate and cesium organic salts attached to a cesium cation [Cs(CsNO 3 )(CsA)] + (A = benzoate, salicylate, hydrogen phthalate, hydrogen maleate, hydrogen fumarate, hydrogen oxalate, and hydrogen malonate ion). These mixed clusters were generated by electrospray from methanol solutions containing cesium nitrate and an organic acid. Collision‐induced dissociation of [Cs(CsNO 3 )(CsA)] + in a quadrupole ion trap gave [Cs(CsNO 3 )] + and [Cs(CsA)] + as major product ions. Loss of HNO 3 was observed, and also CO 2 loss in the case of A = hydrogen malonate. Branching ratios for the dissociation into [Cs(CsNO 3 )] + and [Cs(CsA)] + were treated by the Cooks' kinetic method to obtain a quantitative order of bonding energetics (enthalpies and Gibbs free energies) between Cs + and the molecular salt (ion pair) CsA, and were correlated with the corresponding values calculated using DFT. The kinetic method leads to relative scales of Cs + affinities and basicities that are consistent with the DFT‐calculated values. This study brings new data on the strong interaction between the cesium cation and molecular salts CsA. Copyright © 2006 John Wiley & Sons, Ltd.