Experiment and Curve Fitting

The experimental arrangement has been described previously [229]. The polymer films were irradiated at 248 nm at a pulse repetition rate of 1 Hz to avoid accumulative heating. Emissions were detected with a quadrupole mass spectrometer mounted with the ionizer 30 cm from the sample. Time- 

The model employed below assumed that the emission intensity of the slow component was controlled by a thermally activated process (which we assume is decomposition rate but could be diffusion limited) which continued after the laser pulse. That is, the emission rate, S(t ) is given by  

To predict the actual detected signal, 7(f), at the detector position relative to the sample (x,y,z), the emitted rate was convoluted with the Maxwell-Boltzmann velocity distribution, MB(f-f)  

and a were determined by least squares fitting techniques [230]. 

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