How Collective Phenomena Impact CO Reactivity and Speciation in Different Media.

CO has attracted considerable attention in recent years due to its role in the greenhouse effect and environmental management. While its reaction with water has been studied extensively, the same cannot be said for reactivity in the supercritical CO phase, where the conjugate acid/base equilibria proceed through different mechanisms and activation barriers. In spite of the apparent simplicity of the CO + HO reaction, the collective effect of different environments has a drastic influence on the free energy profile. Enhanced sampling techniques and well-tailored collective variables provide a detailed picture of the enthalpic and entropic drivers underscoring the differences in the formation mechanism of carbonic acid in the gas, aqueous, and supercritical CO phases.