Correlated Molecular Orbital Theory Study of the Al + CO 2 Reaction
Density functional theory (DFT) and correlated molecular orbital electronic structure calculations were used to study the Al + CO → 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 we...
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Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2018-01, Vol.122 (3), p.859-868 |
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Hauptverfasser: | , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Density functional theory (DFT) and correlated molecular orbital electronic structure calculations were used to study the Al + CO
→ 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 + CO
reaction surface to date and are based on consistent application of high-level methods for all stationary points identified. The pathways from Al + CO
to AlO + CO on the electronic ground-state PES all involve formation of one or more stable AlCO
complexes denoted η-AlCO
, trans-AlCO
, and C
-AlCO
, among which η-AlCO
and C
-AlCO
are the least and most stable, respectively. We report a new minimum-energy pathway for the overall reaction, namely formation of η-AlCO
from reactants and dissociation of that same complex to products via a bond-insertion reaction that passes through a fourth (weakly metastable) AlCO
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 CO
is discussed in the context of analogous processes for boron and first-row transition metals. |
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ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/acs.jpca.7b11443 |