The generalized optical interference model for interfacial contributions to vibrational sum frequency generation (VSFG) spectroscopic signals from organic thin film systems is extended to include a description of optical interferences contained in the thin film bulk response. This is based on electric quadrupolar interactions with the input fields and includes a discussion on possible contribution from the electric quadrupolar polarization. VSFG data from the first of this two part report are analyzed and include effects from higher order responses, for both bulk and higher order interfacial terms. The results indicate that although it is capable of capturing many of the data features, the electric dipole treatment is likely not a complete description of the VSFG intensity data from this system. An analysis based on the signs of the resulting response amplitudes is used to deduce the relative magnitude of the electric dipole and higher order interfacial terms. It is found that the buried interface is closer to satisfying the electric dipole approximation, consistent with smaller field gradients due to closer index matching between the organic thin film and substrate relative to air. The procedure outlined in this work allows for the difficult task of deducing a physical picture of average molecular orientation at the buried interface of a multilayer organic thin film system while including higher order effects.
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