Journal of Physical Chemistry, Vol.100, No.43, 17226-17231, 1996
Quenching of O-2(A(1)Delta(G)) by O-2(A(1)Delta(G)) in Solution
The reaction in which O-2(a(1) Delta(g)) is quenched by another O-2(a(1) Delta(g)) molecule is examined in CS2. Spectroscopic data indicate that energy-pooling to form O-2(b(1) Sigma(g)(+)) occurs in this process. This observation is important to the kinetics of O-2(a(1) Delta(g))-O-2(a(1) Delta(g)) annihilation because O-2(b(1) Sigma(g)(+)) is itself a precursor of O-2(a(1) Delta(g)). An upper limit of (7.0 +/- 0.8) x 10(5) s(-1) M(-1) is determined for the O-2(a(1) Delta(g))-O-2(a(1) Delta(g)) annihilation rate constant. Data are also presented to indicate that the quenching of O-2(b(1) Sigma(g)(+)) by the fullerene C-60 is limited by solute diffusion. This result is not consistent with a mechanism of electronic-to-vibrational energy transfer, which thus far has been the only documented deactivation process for O-2(b(1) Sigma(g)(+)) in solution. O-2(b(1) Sigma(g)(+)) quenching by C-60 likely proceeds via electronic energy transfer facilitated by the near degeneracy of the O-2(b(1) Sigma(g)(+)) and triplet C-60 energy levels.
Keywords:SINGLET MOLECULAR-OXYGEN;DIMOL-SENSITIZED LUMINESCENCE;PHASE-PHOTOSENSITIZED REACTIONS;PULSED LASER EXCITATION;TRIPLET-STATE;EXCITED-STATE;1;4-DIMETHYLNAPHTHALENE ENDOPEROXIDE;COLLISIONAL DEACTIVATION;CHEMI-LUMINESCENCE;ENERGY-TRANSFER