Collision-induced electronic transitions in complexes between benzene and molecular oxygen Original Research Article

The collision-induced electric dipole transition moments for the O2 + C6H6 complex have been investigated by the multi-configurational self-consistent field linear response method. Cooperative simultaneous transitions, (1Δg, 3B1u) ← (3Σg−1, A1g) and (1Δg, 3E1u) ← (3Σg−1, A1g), as well as singlet-triplet and singlet-singlet transitions in each molecule have been studied in gas phase and in solvent phase as modelled by a self-consistent reaction field method. Strong intensity enhancement, respectively, reduction is predicted for the 3B1u ← 1A1g and 1E1u ← 1A1g transitions in benzene colliding with oxygen in gas or solvent environments. We find that transitions involving singlet molecular oxygen are greatly enhanced at intermolecular distances easily reached at normal temperature conditions; the b1Σg+ − a1Δg, a1Δg − X3Σg− and b1Σg+ − X3Σg− transition probabilities are predicted to become enhanced approximately by 105, 103 and 100 times in O2 + C6H6 collisions. The enhancement is of such a magnitude that singlet molecular oxygen should be easy to detect by absorption and emission experiments tuned to the particular frequencies. It is argued that the benzene molecule is the most efficient choice among a set of organic colliders for promoting intensity of the Herzberg III band in molecular oxygen.