Deconvolution can be used in electrooptic studies to correct for non-idealelectric excitation pulses only when the electric dipole moment of the studied molecules is predominantly induced

The electric field pulses used for most measurements of transient electroop tic properties such as birefringence and dichroism, are rectangular and ass umed to be ideal, but in practice do all such pulses have non-zero rise and fall times. Claims have been made that this non-ideality may be taken into account by employing standard deconvolution techniques. We find that this approach yields exact results in the zero electric field limit when the ele ctric dipole moment of the studied macromolecules is predominantly induced. However, for finite electric field strengths and/or macromolecules with pa rtly or fully permanent electric dipole moments, we find that the deconvolu tion method yields erroneous estimates of the electrooptic relaxation times . When the decay time of the electric pulse and the electrooptic decay time are equal, and the system is operated in the Kerr domain, this systematic error for macromolecules with purely permanent electric dipole moment equal s 37%. In a research field where the uncertainty of the reported relaxation times normally is assumed to be only a Few percent this is an error that m ay seriously mislead unsuspecting users. We find that this systematic error can readily be avoided by employing standard numerical integration of a se t of coupled first-order differential equations instead of the standard dec onvolution techniques. (C) 2000 Elsevier Science B.V. All rights reserved.