Journal of Chemical Physics, Vol.110, No.3, 1628-1632, 1999
Deterministic identifiability of photophysical kinetic models with transients via the method of similarity transformation
The method of similarity transformation is shown to be applicable to the problem of deterministic identifiability of photophysical kinetic models with transients. A two-state excited-state model of irreversible intermolecular association with transients is demonstrated to be identifiable from two decay traces at two observation wavelengths and one co-reactant concentration, when either only the species that associates with the co-reactant is directly excited or the excited species spectra are separated such that each species can be monitored individually. When transients are absent, two decays at one co-reactant concentration do not guarantee the recovery of the model parameters, which indicates that transient effects change identifiability criteria compared to the case with time-invariant rate constants.
Keywords:EXCITED-STATE PROCESSES;GLOBAL COMPARTMENTAL ANALYSIS;FLUORESCENCE DECAY SURFACE;NONSTATIONARY DIFFUSION-MODEL;REACTION SYSTEMS;RATE CONSTANTS;QUENCHER;DISTINGUISHABILITY;BOUNDS;VERIFY