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Femtosecond hyper‐Rayleigh scattering has recently been used to determine the spatial correlation length between nonlinear optical chromophores in polymer films [G. Olbrechts et al., Chem. Phys. Lett. 253, 135 (1996)]. This correlation length corresponds to the effective interaction length for frequency doubling in waveguide format, as derived from phase‐matching curves. The temporal characteristics of this correlation length have now been studied and compared with thermal relaxation times, obtained with coherent second‐harmonic generation. The correlation length decays much faster than the second‐harmonic intensity, indicating that the efficiency of a second‐order waveguide process could decay much faster than generally anticipated. © 1996 American Institute of Physics.