TY - JOUR
T1 - Correlated Molecular Orbital Theory Study of the Al + CO2 Reaction
AU - Chitsazi, Rezvan
AU - Veals, Jeffrey D.
AU - Shi, Yi
AU - Sewell, Tommy
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/25
Y1 - 2018/1/25
N2 - Density functional theory (DFT) and correlated molecular orbital electronic structure calculations were used to study the Al + CO2 → AlO + CO reaction on the electronic ground-state potential-energy surface (PES). Geometries were optimized using DFT (M11/jun-cc-pV(Q+d)Z) and more accurate energies were obtained using the composite Weizmann-1 theory with Brueckner doubles (W1BD). The results comprise the most complete, most systematic characterization of the Al + CO2 reaction surface to date and are based on consistent application of high-level methods for all stationary points identified. The pathways from Al + CO2 to AlO + CO on the electronic ground-state PES all involve formation of one or more stable AlCO2 complexes denoted η-AlCO2, trans-AlCO2, and C2v-AlCO2, among which η-AlCO2 and C2v-AlCO2 are the least and most stable, respectively. We report a new minimum-energy pathway for the overall reaction, namely formation of η-AlCO2 from reactants and dissociation of that same complex to products via a bond-insertion reaction that passes through a fourth (weakly metastable) AlCO2 complex denoted cis-OAlCO. Natural Bond Orbital analysis was applied to study trends in charge distribution and the degree of charge transfer in key structures along the minimum-energy pathway. The process of aluminum insertion into CO2 is discussed in the context of analogous processes for boron and first-row transition metals.
AB - Density functional theory (DFT) and correlated molecular orbital electronic structure calculations were used to study the Al + CO2 → AlO + CO reaction on the electronic ground-state potential-energy surface (PES). Geometries were optimized using DFT (M11/jun-cc-pV(Q+d)Z) and more accurate energies were obtained using the composite Weizmann-1 theory with Brueckner doubles (W1BD). The results comprise the most complete, most systematic characterization of the Al + CO2 reaction surface to date and are based on consistent application of high-level methods for all stationary points identified. The pathways from Al + CO2 to AlO + CO on the electronic ground-state PES all involve formation of one or more stable AlCO2 complexes denoted η-AlCO2, trans-AlCO2, and C2v-AlCO2, among which η-AlCO2 and C2v-AlCO2 are the least and most stable, respectively. We report a new minimum-energy pathway for the overall reaction, namely formation of η-AlCO2 from reactants and dissociation of that same complex to products via a bond-insertion reaction that passes through a fourth (weakly metastable) AlCO2 complex denoted cis-OAlCO. Natural Bond Orbital analysis was applied to study trends in charge distribution and the degree of charge transfer in key structures along the minimum-energy pathway. The process of aluminum insertion into CO2 is discussed in the context of analogous processes for boron and first-row transition metals.
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U2 - 10.1021/acs.jpca.7b11443
DO - 10.1021/acs.jpca.7b11443
M3 - Article
C2 - 29240423
AN - SCOPUS:85041181648
SN - 1089-5639
VL - 122
SP - 859
EP - 868
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 3
ER -