Activation energy singlet

FIGURE 9 Thermal activation energies (singlet-triplet resp. singlet-quintet energy separation) of the ESR spectra. 

Fig. 3 A schematic illustration of through-bond and through-space interactions between the radical centers. The singlet-triplet energy gap, the activation energy (E, and the energy...

Works [40, 91] surveyed y versus temperature for deactivation of 02( Aj ) on quartz at 350- 900 K. The obtained temperature dependencies were in the Arrhenius form with the activation energy of 18.5kJ/mole. A conclusion was drawn up about the chemisorption mechanism of singlet oxygen deactivation on quartz surface. A similar inference was arrived at by the authors of work [92] relative to 02( A ) deactivation (on a surface of oxygen-annealed gold). 

For an oxidized surface, the value of y is 10" - 1.7-10 and it decreases with increasing the experimental temperature. In this case the activation energy of a change in yis 2.1 kcal/mole. From these data it can be inferred that the heterogeneous de-excitation of singlet oxygen proceeds in terms of the physical adsorption mechanism similar to that described for glass. 

This conclusion is in agreement with experiments in which a smootb quartz and cellulose were used as substrates. For above materials the transfer of excitation energy of the dye into the substrate is low which is confirmed by intensive luminescence of adsorbed tripaflavine. Note, that the activation energy of emission of singlet oxygen is close for zinc oxide oxidized by oxygen atoms, quartz and cellulose and amounts to 5-10 kcal/mol [83]. 

Sulfur tetrafluoride appears as two broad singlets at room temperature, as one broad singlet at 85 °C, and (when dry) as two sharp triplets at -30 °C. SF6, with its symmetrical octahedral geometry, appears as a sharp singlet at all temperatures. The activation energy for pseudorotation of SF4, which interconverts its axial and equatorial fluorines, is 12kcalmor1.3... 

Preliminary calculations of reaction paths have proved encouraging. Thus singlet carbene is predicted to insert into CH bonds, and to add to double bonds, by concerted processes involving no activation the critical geometries are as indicated in 32 and 33. The latter is of course that predicted by Skell56) and supported experimentally by ClossS7) it is also in accord with predictions based on considerations of orbital symmetry or Evans principle 31). The total lack of discrimination shown by carbene in reactions of this type also indicates that the activation energies must be zero or close to zero. 

Figure 1. Adiabatic potential curves in the main chain scission of a model compound of poly(isobutylene) 2,2-, 4,4-tetramethylpentane (4). AE3l(=0.61eV), aET,(—0.35eV), and AEf (=2.05eV) are the activation energies of the main chain scission in the lowest singlet excited state (S,), the lowest triplet state (T,), and the ground state, respectively.

---