CIDEP Spectrum Escaped 2-Propanolyl Radicals

For the purpose of this work, no attempt to model the lineshape is made but rather to simply calculate the phase and magnitude of the polarisation. The EPR spectrum is calculated from the accumulated populations of the spin states on the escaped 2-propanolyl radicals during the simulation and averaged over a large number of realisations. The relative intensity of each peak can be calculated as 

In this expression, i and j are the eigenstates, pi and pj represent the population of the spin states and 5+ is the raising spin operator. To compute the standard deviation in the intensity, the population of the spin states of the escaped 2-propanolyl radicals, together with the square of the populations were accumulated after every realisation and averaged over the total number of realisations. The variance in the intensity can be calculated to be 

All the results presented for E(/) are reported to 84 % confidence, with the sign of the polarisation identified within reasonable confidence limits. 

As previously mentioned, all simulations were done using the Slice package and wherever possible repeated with the Hybrid program as a way of verilying the results. Unless otherwise mentioned, the spin parameters used in the simulation are those detailed in Table 5.3 and the kinetic parameters are those detailed in Table 5.4 (diffusion controlled conditions) or Table 5.5 (partially diflusion controlled conditions). The initial nuclear spin configuration was selected randomly at the start of every 

---