[Zurück]

X. Li, G. Rupprechter:
"A modeling analysis of molecular orientation at interfaces by polarization-dependent sum frequency generation vibrational spectroscopy";
Chinese Journal of Catalysis, 40 (2019), 11; S. 1655 - 1667.

Sum frequency generation (SFG) vibrational spectroscopy has been proven an excellent tool to
measure the molecular structures, symmetries and orientations at surfaces/interfaces because of its
strong polarization dependence. However, a precise quantitative analysis of SFG spectral intensity
and molecular orientation at interfaces must be carefully performed. In this work, we summarized
the parameters and factors that are often ignored and illustrated them by evaluating studies of CO
adsorption on the (111) facet of platinum (Pt) and palladium (Pd) single crystals at the gas (ultra-
high vacuum, UHV)/solid interfaces and methanol (water) adsorption at the air/liquid (solid/
liquid) interfaces in the presence of sodium iodide (chloride) salts. To intuitively estimate the
influence of incidence angles and refractive indices on the SFG intensity, solely a defined factor of
|F_yyz| was discussed, which can be individually separated from the macroscopic second-order
non-linear susceptibility X_yyz(2) term and represents the SSP intensity. Moreover, effects of refractive
indices and the molecular hyperpolarizability ratio (R) were discussed in the orientational analysis
of interfacial CO and methanol molecules. When I_PPP/I_SSP was identical, molecules with a larger R had
smaller tilting angles (θ) on Pt (assuming θ < 51°), and CO molecules on Pd would tilt much closer to
the surface than they did on Pt. A total internal reflection (TIR) geometry enhanced the SFG intensity,
but it also amplified the influence of refractive index on SFG intensity at the solid (silica)/liquid
interface. The refractive index and R-value had similar influence on the methanol orientation in the
presence of sodium iodide salts at air/liquid and solid/liquid interfaces. This work should provide a
guideline for analyzing the orientation of molecules with different R, which are adsorbed on catalysts
or located at liquid interfaces involving changes of refractive indices.

http://dx.doi.org/10.1016/S1872-2067(19)63357-7