Nonlocal photopolymerization kinetics including multiple termination mechanisms and dark reactions. Part I. Modeling

The photochemical processes present during free-radical-based holographic grating formation are examined. A kinetic model is presented, which includes, in a more nearly complete and physically realistic way, most of the major photochemical and nonlocal photopolymerization-driven diffusion effects. These effects include: (i) nonsteady-state kinetics (ii) spatially and temporally nonlocal polymer chain growth (iii) time varying photon absorption (iv) diffusion controlled viscosity effects (v) multiple termination mechanisms, and (vi) inhibition. The convergence of the predictions of the resulting model is then examined. Comparisons with experimental results are carried out in Part II of this series of papers [J. Opt. Soc. Am. B 26, 1746 (2009)].