Direct Spectroscopic Measurement of Interfacial Electric Fields near an Electrode under Polarizing or Current-Carrying Conditions
By Patrow, Joel G.; Sorenson, Shayne A.; Dawlaty, Jahan M.
Published in The Journal of Physical Chemistry C
NULL
2017
Abstract
Interfacial electric fields and the related molecular polarization are the central quantities that govern charge transfer between an electrode and a molecule. The presence of the interfacial field is often inferred indirectly through transport and capacitance measurements. It is desirable to measure such fields directly via the Stark shift that they induce on molecular vibrations. We report the Stark shift of a well-known vibrational chromophore tethered near an electrochemical interface measured using vibrational sum frequency generation spectroscopy. We have two important findings. First, we observe that the measured local field scales with respect to the ionic concentration in the electrolyte according to a model that combines the Gouy
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