Inferring the Energetics of CO 2 -Aniline Adduct Formation from Vibrational Spectroscopy.

Control of atmospheric CO 2 is an important contemporary scientific and engineering challenge. Toward this goal, the reaction of CO 2 with amines to form carbamate bonds is an established method for CO 2 capture. However, controllable reversal of this reaction remains difficult and requires tuning the energetics of the carbamate bond. Through IR spectroscopy, we show that a characteristic frequency observed upon carbamate formation varies as a function of the substituent's Hammett parameter for a family of para -substituted anilines. We present computational evidence that the vibrational frequency of the adducted CO 2 serves as a predictor of the energy of formation of the carbamate. Electron donating groups typically enhance the driving force of carbamate formation by transferring more charge to the adducted CO 2 and thus increasing the occupancy of the antibonding orbital in the carbon-oxygen bonds. Increased occupancy of the antibonding orbital within adducted CO 2 indicates a weaker bond, leading to a red-shift in the characteristic carbamate frequency. Our work serves the large field of CO 2 capture research where spectroscopic observables, such as IR frequencies, are more easily obtainable and can stand in as a descriptor of driving forces.