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 CO2 + aqueous amine reaction. Previous errors of over 10 kcal mol(-1) are revealed. Activation energies were also estimated with semicontinuum modeling, and a refined discussion of the competing hypothetical mechanisms for CO2 + monoethanolamine (MEA) is presented. Further results are also presented to demonstrate that the basicity of an amine (aqueous proton affinity) correlates only with CO2 affinity within an amine class: secondary amines have an extra CO2 affinity that primary amines do not have.