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The internal energy dynamics of three examples of PAHs are probed using a high resolution energy time of flight spectrometer. The measured H-loss rates are converted to internal energy values for a range of UV photon wavelengths. Multi step multi photon absorption scheme is proposed to estimate the possible internal energy values with reasonable accuracies. This was possible because of the ultrafast radiationless internal conversion process in PAHs and their structural rigidity. Thus, a method is proposed to produce PAH cations with narrow and known internal energy distribution using a single nanosecond pulsed laser, paving a way to study statistical unimolecular decay in PAHs very efficiently. [ABSTRACT FROM AUTHOR]