On the existence of CO32− microsolvated clusters: a theoretical study

Abstract

Microsolvated clusters of multiply charged anions play a crucial role in atmospheric chemistry and some of them were previously registered experimentally. At the same time, there are no experimental observations of [CO₃·(H₂O)_n]²⁻. The reasons for this may be related to the thermodynamical or kinetical instability of microsolvated CO₃²⁻ toward autoionization or autoprotonation processes. In this study we theoretically investigate the potential stability of the [CO₃·(H₂O)_n]²⁻ microsolvated clusters from both perspectives – thermodynamic and kinetic – and we claim they are stable toward autoionization and kinetically semi-stable toward autoprotonation. In addition, the behaviour of CO₃²⁻ anions in bulk water solvent was analysed to highlight important precautions for synthetic purposes.