The Solvation of Ca²⁺ with Gas Phase Clusters of Alcohol Molecules

A comprehensive examination of how the identity of an alcohol molecule can change the behavior of a solvated, alkaline earth dication has been undertaken. The metal dication of Ca²⁺ has been clustered with a range of different alcohols to form [Ca(ROH)_n]²⁺ complexes, where n lies in the range 2-20. Following collisional activation via electron capture from nitrogen gas, complexes for n in the range 2-6 exhibit a switch in reaction product as a function of n. For low values, solvated CaOH⁺ is the dominant fragment, but as n increases beyond 4, this is displaced by the appearance of solvated CaOR⁺. A separate study of unimolecular metastable decay by [Ca(ROH)_n]²⁺ complexes found evidence of charge separation to form CaOH⁺(ROH)_n-1 + R⁺. For two isomers of butanol, the n = 3 complexes were found to follow parallel, but different metastable pathways: one leading to the appearance of CaOH⁺ and another that resulted in proton abstraction to form ROH₂⁺. These differences have been attributed to the precursor complexes adopting geometries where one ROH molecule occupies a secondary solvation shell. Comparisons were made with a previous study of magnesium complexes; [Mg(ROH)_n]²⁺ show that the difference in second ionization energy Mg⁺ (15.09 eV) as opposed to Ca⁺ (11.88 eV) influences behavior. A complex between Ca²⁺ and 1-chloroethanol is shown to favor the formation of CaCl⁺ as opposed to CaOH⁺ as a unimolecular charge separation product, which is attributed to differences in bond energy in the precursor molecule.