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Recently, continuum Microkinetic Rate Theory (cMRT) has been advanced as amethod of studying rates of systems, where deviations between observation andcMRT theory have been found, and it hypothesized that these deviations arelinked either to oscillations or fluctuations. Multinomial probability theory(MPT) is used to derive analytical expressions for concentration fluctuations,giving the fluctuations as a function of average concentrations and samplesizes. MPT predictions of fluctuations in kinetically constrained systems areverified against kinetic Monte Carlo, and it analytically shown that MPTpredicts canonical and grand canonical ensemble fluctuations. These fluctuationresults are discussed in conjunction with cMRT deviations and it argued thatfluctuations are not responsible for the deviations.

Concentration Fluctuations from Multinomial Probability Theory and the possible role in continuum Microkinetic Rate Theory