Bonding analysis of the [C(2)O(4)](2+) intermediate formed in the reaction of CO(2)(2+) with neutral CO(2).
The bonding patterns of the [C(2)O(4)](2+) dication formed upon interaction of CO(2)(2+) with neutral CO(2) 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 CO(2)(+) monocations formed in the thermal reaction CO(2)(2+) + CO(2) --> [C(2)O(4)](2+) --> 2 CO(2)(+), specifically that the CO(2)(+) monocation formed from the dication dissociates far more readily than the CO(2)(+) monocation formed from the neutral molecule. The bonding pattern is consistent with a description of intermediate [C(2)O(4)](2+) as a complex between the triplet ground state of CO(2)(2+) with the singlet ground state of neutral CO(2), which can, among other pathways, smoothly proceed to a nondegenerate pair of (4)CO(2)(+) + (2)CO(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 [C(2)O(4)](2+) intermediate. In addition, dissociation of (4)CO(2)(+) is discussed based on CCSD and CASSCF calculations. Equilibrium geometries for the ground electronic states of CO(2)(0/+/2+) and some other relevant structures of CO(2)(+) are determined using the MRCI method.
Feixas
Ferran
F
Institute of Process Fundamentals, Academy of Sciences of the Czech Republic, Rozvojova 135, 165 02, Prague 6, Suchdol 2, Czech Republic.
Ponec
Robert
R
Fiser
Jirí
J
Roithová
Jana
J
Schröder
Detlef
D
Price
Stephen D
SD