We have recently developed a new singularity‐free algorithm for Brownian dynamics simulation of free rotational diffusion. The algorithm is rigorously derived from kinetic theory and makes use of the Cartesian components of the rotation vector as the generalized coordinates describing angular orientation. Here, we report on the application of this new algorithm in Brownian dynamics simulations of transient electro‐optical properties. This work serves two main purposes. Firstly, it demonstrates the integrity of the new algorithm for BD‐simulations of the most common transient electro‐optic experiments. Secondly, it provides new insight into the performance of the new algorithm compared to algorithms that make use of the Euler angles. We study the transient electrically induced birefringence in dilute solutions of rigid particles with anisotropic polarization tensor in response to external electric field pulses. The use of both one single electric pulse and two electric pulses with opposite polarity are being analyzed. We document that the new singularity‐free algorithm performs flawlessly. We find that, for these types of systems, the new singularity‐free algorithm, in general, outperforms similar algorithms based on the Euler angles. In a wider perspective, the most important aspect of this work is that it serves as an important reference for future development of efficient BD‐algorithms for studies of more complex systems. These systems include polymers consisting of rigid segments with single‐segment translational–rotational coupling, segment–segment fluid‐dynamic interactions and holonomic constraints.
