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Non-local photopolymerization kinetics with multiple termination mechanisms and post-exposure effects

The one-dimensional Non-local Photo-Polymerization Driven Diffusion (NPDD) model, which governs the temporal evolution of holographic grating formation in photopolymers, has been further developed to include all major photochemical processes. These effects include: i) non-steady state kinetics, ii) spatially non-local polymer chain growth, iii) time varying photon absorption, iv) diffusion controlled effects, v) multiple termination mechanisms, vi) inhibition, and vii) post-exposure or dark-reaction effects. The resulting analytic expressions for the monomer and polymer concentrations are then derived and their validity tested against experimental data using a 4-harmonic, numerical fitting regime. The temporal variation in the refractive index modulation is accounted for using the Lorentz- Lorenz relation, and the effects of dark reactions for short holographic exposures are examined for a range of photopolymer materials.