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We have studied the cluster structure of 1-butyl-3-methylimidazolium halide, bmimX (X = Cl, Br, I), in methanol solution by means of an electrospray mass spectrometer, which is specially designed for analysis of clusters isolated from solution. In positive ion mode experiments, the ratio of solvated bmim(+), bmim(+)(MeOH)(n) and ion-pair clusters, bmim(bmim(+)X(-))(m) was dependent on the counter anion. As for bmimCl solutions, few solvated bmim(+) clusters were observed, and the ion-pair clusters were clearly observed. On the other hand, bmimBr and bmimI with large anions, the solvated bmim(+) clusters increased obviously, and the ion-pair clusters were in turn remarkably decreased. In negative ion-mode experiments, the solvation for Br(-) by the methanol is found to be the most prominent among those for Cl(-), Br(-), and I(-). These results were reasonably explained in consideration of the balance between ion-solvent and ion-counterion interactions.

Microscopic structures of 1-butanol (1-BuOH)–water mixtures in the presence and absence of salts are studied through the mass spectrometric analysis of clusters generated from the fragmentation of liquid droplets. The analysis of cluster structures provides information on the phase separation of 1-BuOH–water mixtures from the microscopic viewpoint. In a saturated solution of 1-BuOH in water, 1-BuOH exists as hydrated 1-BuOH clusters and self-associated 1-BuOH clusters. With further addition of 1-BuOH, a 1-BuOH rich phase is generated. When the salt (LiCl, NaCl, MgCl2, etc.) coexists in the 1-BuOH–water mixtures, the cation is preferentially solvated by the 1-BuOH to form M +(1-BuOH) m or M 2+(1-BuOH) m clusters: M + = Li+, Na+, Mg2+ = Mg2+, etc., m = 1, 2, 3, ... Since the formation of M +(1-BuOH) m corresponds to an increase of the self-associated 1-BuOH clusters in water, the presence of the salt induces the phase separation at lower 1-BuOH concentrations.

We here report a comparative experimental and theoretical study of dipole-bound electron attachment on four polar hydrogen-bonded dimers containing one water molecule (water-water, ammonia-water, phenol-water and pyridine-water). When the water molecule is the proton acceptor in the neutral complex, with a trans-linear hydrogen bond (water-water and phenol-water), it is shown that the equilibrium geometry of the dipole-bound anion tends to a cis-linear hydrogen bond for which the total dipole moment is larger. On the contrary, when the water molecule is the proton donor to a nitrogen atom (ammonia-water and pyridine-water), dipole-bound electron attachment does not lead to subsequent modifications of the complex geometry.