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

0344001 - ÚCHP 2011 RIV US eng J - Journal Article
Feixas, F. - Ponec, Robert - Fišer, J. - Roithová, J. - Schröder, Detlef - Price, S.D.
Bonding Analysis of the [C2O4]2+ Intermediate Formed in the Reaction of CO2 2+ with Neutral CO2.
Journal of Physical Chemistry A. Roč. 114, č. 24 (2010), s. 6681-6688. ISSN 1089-5639. E-ISSN 1520-5215
R&D Projects: GA ČR GA203/09/1223; GA ČR GA203/09/0118
Grant - others:MICINN(ES) AP2005-2997
Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z40550506
Keywords : fermi holes * bonding pattern * neutral reactant
Subject RIV: CC - Organic Chemistry
Impact factor: 2.732, year: 2010

The bonding pattern is consistent with a description of intermediate [C2O4]2+ as a complex between the triplet ground state of CO2 2+ with the singlet ground state of neutral CO2, which can, among other pathways, smoothly proceed to a nondegenerate pair of 4CO2 + + 2CO2 + 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 4CO2 + is discussed based on CCSD and CASSCF calculations. Equilibrium geometries for the ground electronic states of CO2 0/+/2+ and some other relevant structures of CO2+ are determined using the MRCI method.
Permanent Link: http://hdl.handle.net/11104/0005932