Reductions of oxygen, carbon dioxide, and acetonitrile by the magnesium(II)/magnesium(I) couple in aqueous media: theoretical insights from a nano-sized water droplet.
Reductions of O2, CO2, and CH3CN by the half-reaction of the Mg(II)/Mg(I) couple (Mg(2+) + e(-) → Mg(+•)) confined in a nanosized water droplet ([Mg(H2O)16](•+)) have been examined theoretically by means of density functional theory based molecular dynamics methods. The present works have revealed many intriguing aspects of the reaction dynamics of the water clusters within several picoseconds or even in subpicoseconds. The reduction of O2 requires an overall doublet spin state of the system. The reductions of CO2 and CH3CN are facilitated by their bending vibrations and the electron-transfer processes complete within 0.5 ps. For all reactions studied, the radical anions, i.e., O2(•-), CO2(•-), and CH3CN(•-), are initially formed on the cluster surface. O2(•-) and CO2(•-) can integrate into the clusters due to their high hydrophilicity. They are either solvated in the second solvation shell of Mg(2+) as a solvent-separated ion pair (ssip) or directly coordinated to Mg(2+) as a contact-ion pair (cip) having the (1)η-[MgO2](•+) and (1)η-[MgOCO](•+) coordination modes. The (1)η-[MgO2](•+) core is more crowded than the (1)η-[MgOCO](•+) core. The reaction enthalpies of the formation of ssip and cip of [Mg(CO2)(H2O)16](•+) are -36 ± 4 kJ mol(-1) and -30 ± 9 kJ mol(-1), respectively, which were estimated based on the average temperature changes during the ion-molecule reaction between CO2 and [Mg(H2O)16](•+). The values for the formation of ssip and cip of [Mg(O2)(H2O)16](•+) are estimated to be -112 ± 18 kJ mol(-1) and -128 ± 28 kJ mol(-1), respectively. CH3CN(•-) undergoes protonation spontaneously to form the hydrophobic [CH3CN, H](•). Both CH3CN and [CH3CN, H](•) cannot efficiently penetrate into the clusters with activation barriers of 22 kJ mol(-1) and ∼40 kJ mol(-1), respectively. These results provide fundamental insights into the solvation dynamics of the Mg(2+)/Mg(•+) couple on the molecular level.
Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China.
Tim-Wai
TW
Lam
Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China.
Han
H
Zhang
Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China.
Chi-Kit
CK
Siu