Solution

ID: past-exam-of-the-chemistry-course-of-the-year-1-of-the-natural-sciences-course-of-the-university-of-cambridge/2024/paper-1/2/a/i/solution

Carbon dioxide is linear, with two equivalent C–O bonds of formal bond order two; its Homo is predominantly oxygen nonbonding and its LUMO is C–O antibonding. The carbon uses two opposite hybrids for its sigma bonds and two perpendicular p atomic orbitals for pi bonding. A localized picture assigns each terminal oxygen an sigma/lone-pair framework and one p orbital for its local pi bond.
In a symmetry-adapted description, each of the two perpendicular sets of oxygen and carbon p functions forms bonding, oxygen-centred nonbonding and antibonding combinations. The occupied nonbonding pair is labelled and the lowest empty pi pair . The latter has appreciable amplitude at carbon, explaining its electrophilic reactivity. Hybridization of a terminal atom with only one bonded neighbour is a choice of localized basis, not an independently measurable bond angle; an alternative oxygen plus p basis can represent the same delocalized system.
There are 16 valence electrons: four in the two sigma bonds, four in the two net pi bonds, and eight in the remaining oxygen lone-pair combinations. These local electron counts and the delocalized orbital description are alternative bookkeeping schemes, not additional electrons.

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