Semicontinuum Solvation Modeling Improves Predictions
of Carbamate Stability in the CO<sub>2</sub> + Aqueous Amine Reaction
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Abstract
Quantum
chemistry computations with a semicontinuum (cluster +
continuum) solvation model have been used to cure long-standing misprediction
of aqueous carbamate anion energies in the industrially important
CO<sub>2</sub> + aqueous amine reaction. Previous errors of over 10
kcal mol<sup>–1</sup> are revealed. Activation energies were
also estimated with semicontinuum modeling, and a refined discussion
of the competing hypothetical mechanisms for CO<sub>2</sub> + monoethanolamine
(MEA) is presented. Further results are also presented to demonstrate
that the basicity of an amine (aqueous proton affinity) correlates
only with CO<sub>2</sub> affinity within an amine class: secondary
amines have an extra CO<sub>2</sub> affinity that primary amines do
not have
