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Bonding Analysis of the [C2O4](2+) Intermediate Formed in the Reaction of CO22+ with Neutral CO2

Feixas, F; Ponec, R; Fiser, J; Roithova, J; Schroder, D; Price, SD; (2010) Bonding Analysis of the [C2O4](2+) Intermediate Formed in the Reaction of CO22+ with Neutral CO2. J PHYS CHEM A , 114 (24) 6681 - 6688. 10.1021/jp1020559.

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Abstract

The bonding patterns of the [C2O4](2+) dication formed upon interaction of CO22+ with neutral CO2 are investigated using the analysis of domain-averaged Fermi holes (DAFHs). The DAFH approach provides an explanation for the previously observed "asymmetry" of the energy deposition in the pair of CO2+ monocations formed in the thermal reaction CO22+ + CO2 -> [C2O4](2+) -> 2 CO2+, specifically that the CO2+ monocation formed from the dication dissociates far more readily than the CO2+ monocation formed from the neutral molecule. The bonding pattern is consistent with a description of intermediate [C2O4](2+) as a complex between the triplet ground state of CO22+ with the singlet ground state of neutral CO2, which can, among other pathways, smoothly proceed to a nondegenerate pair of (CO2+)-C-4 + (CO2+)-C-2 where the former stems from the dication and the latter stems from the neutral reactant. Hence the "electronic history" of the components is retained in the [C2O4](2+) intermediate. In addition, dissociation of (CO2+)-C-4 is discussed based on CCSD and CASSCF calculations. Equilibrium geometries for the ground electronic states of CO20/+/2+ and some other relevant structures of CO2+ are determined using the MRCI method.

Type:Article
Title:Bonding Analysis of the [C2O4](2+) Intermediate Formed in the Reaction of CO22+ with Neutral CO2
DOI:10.1021/jp1020559
Keywords:AVERAGED FERMI HOLES, CHARGE-TRANSFER, CHEMICAL-BONDS, HYPERVALENT MOLECULES, COLLISION ENERGIES, ELECTRONIC STATES, DICATIONS, DISSOCIATION, COMPETITION, DYNAMICS
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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