Abstract
We investigate activation of carbon dioxide by singly charged hydrated magnesium cations Mg .+(H2O)n, through infrared multiple photon dissociation (IRMPD) spectroscopy combined with quantum chemical calculations. The spectra of [MgCO2(H2O)n].+ in the 1250–4000 cm−1 region show a sharp transition from n=2 to n=3 for the position of the CO2 antisymmetric stretching mode. This is evidence for the activation of CO2 via charge transfer from Mg .+ to CO2 for n≥3, while smaller clusters feature linear CO2 coordinated end‐on to the metal center. Starting with n=5, we see a further conformational change, with CO2 .− coordination to Mg2+ gradually shifting from bidentate to monodentate, consistent with preferential hexa‐coordination of Mg2+. Our results reveal in detail how hydration promotes CO2 activation by charge transfer at metal centers.
Highlights
CO2CÀ(H2O)2–61 and (CO2) for n ! 3, while smaller clusters feature linear CO2 coordinated end-on to the metal center
Our results reveal in detail how hydration promotes CO2 activation by charge transfer at metal centers
Due to its infrared (IR) active modes,[1] CO2 is the major contribution to the anthropogenic greenhouse effect.[2]
Summary
CO2 for n ! 3, while smaller clusters feature linear CO2 coordinated end-on to the metal center. We probe CO2 and CO2CÀ vibrational modes as well as H2O bending and stretching modes in the 1250– 4000 cmÀ1 region in an FT-ICR mass spectrometer via infrared multiple photon dissociation (IRMPD) spectroscopy.
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