Most electrochemical processes occur in the electrode-solution interface, thus, understanding the structure and dynamic of the electric double layer is mandatory for the development of the field and its related technologies. Herein, we present an apparatus for in situ ultrafast dynamics and low-frequency stimulated Raman spectroscopy measurements of the electrochemical interface by time-resolved optical Kerr effect spectroscopy. We give details of the laser system, the spectroelectrochemcial cell, and calibration of the integrated setup. We studied the time-resolved measurements as a function of the sample position and the electrochemical potential. Analysis in the time and frequency domain together with root-mean-squared amplitude analysis of the nonlinear signals are shown. The results obtained by femtosecond spectroscopy depends on the electrochemical potential and are discussed in terms of orientation and collective molecular dynamics.
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