Control of atmospheric CO2 is an important contemporary scientific and engineering challenge. Towards this goal, the reaction of CO2 with amines to form carbamate bonds is an established method for CO2 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 CO2 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 CO2 and thus increasing the occupancy of the anti-bonding orbital in the carbon-oxygen bonds. Increased occupancy of the anti-bonding orbital within adducted CO2 indicates a weaker bond, leading to a red shift in the characteristic carbamate frequency. As a result, our work serves the large field of CO2 capture research where spectroscopic observables, such as IR frequencies, are more easily obtainable and can stand in as a descriptor of driving forces.
Delibas, Berk, et al. "Inferring the Energetics of CO<sub>2</sub>–Aniline Adduct Formation from Vibrational Spectroscopy." The Journal of Physical Chemistry A, vol. 127, no. 24, Jun. 2023. https://doi.org/10.1021/acs.jpca.3c01406
Delibas, Berk, Kron, Kareesa J., Cotton, Daniel E., Salazar, Noemi, Sharada, Shaama Mallikarjun, & Dawlaty, Jahan M. (2023). Inferring the Energetics of CO<sub>2</sub>–Aniline Adduct Formation from Vibrational Spectroscopy. The Journal of Physical Chemistry A, 127(24). https://doi.org/10.1021/acs.jpca.3c01406
Delibas, Berk, Kron, Kareesa J., Cotton, Daniel E., et al., "Inferring the Energetics of CO<sub>2</sub>–Aniline Adduct Formation from Vibrational Spectroscopy," The Journal of Physical Chemistry A 127, no. 24 (2023), https://doi.org/10.1021/acs.jpca.3c01406
@article{osti_2997912,
author = {Delibas, Berk and Kron, Kareesa J. and Cotton, Daniel E. and Salazar, Noemi and Sharada, Shaama Mallikarjun and Dawlaty, Jahan M.},
title = {Inferring the Energetics of CO<sub>2</sub>–Aniline Adduct Formation from Vibrational Spectroscopy},
annote = {Control of atmospheric CO2 is an important contemporary scientific and engineering challenge. Towards this goal, the reaction of CO2 with amines to form carbamate bonds is an established method for CO2 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 CO2 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 CO2 and thus increasing the occupancy of the anti-bonding orbital in the carbon-oxygen bonds. Increased occupancy of the anti-bonding orbital within adducted CO2 indicates a weaker bond, leading to a red shift in the characteristic carbamate frequency. As a result, our work serves the large field of CO2 capture research where spectroscopic observables, such as IR frequencies, are more easily obtainable and can stand in as a descriptor of driving forces.},
doi = {10.1021/acs.jpca.3c01406},
url = {https://www.osti.gov/biblio/2997912},
journal = {The Journal of Physical Chemistry A},
issn = {ISSN 1520-5215},
number = {24},
volume = {127},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2023},
month = {06}}