De Novo Determination of Molecular Orientation at Interfaces through Multimode Polarization-Dependent Sum-Frequency Generation Spectroscopy

Many essential processes occur at soft interfaces, from chemical reactions on aqueous aerosols in the atmosphere to biochemical recognition and binding at the surface of cell membranes. The spatial arrangement of molecules specifically at these interfaces is crucial for many of such processes. The accurate determination of the interfacial molecular orientation has been challenging due to the low number of molecules at interfaces and the ambiguity of their orientational distribution. Here, we combine phase- and polarization-resolved sum-frequency generation spectroscopy to obtain the molecular orientation at the interface. We extend an exponentially decaying orientational distribution to multiple dimensions, which, in conjunction with multiple SFG data sets obtained from the different vibrational modes, allows us to determine molecular orientation. We apply this new approach to formic acid molecules at the air-water interface. The inferred orientation of formic acid agrees very well with ab initio molecular dynamics data. The phase-resolved SFG multimode analysis scheme using the multi-dimensional orientational distribution thus provides a universal approach for obtaining the interfacial molecular orientation.

Mid-Infrared Frequency Generation via Intermodal Difference Frequency Generation in AlGaAs-On-Insulator Waveguides

We investigate theoretically mid-infrared (MIR) generation via difference frequency generation in multimode AlGaAs-on insulator (AlGaAs-OI) waveguides. The large refractive index difference between the AlGaAs core and the silica cladding shrinks the modes size down to the sub-μm2 scale, and, together with AlGaAs strong second-order nonlinear polarization, empowers strong nonlinear effects. As a result, efficient MIR generation is obtained in few-cm long waveguides with sub-μm2 transverse section, where higher order modes are exploited to achieve the phase-matching condition. These observations suggest that multimode AlGaAs-OI waveguides could represent a novel promising platform for on-chip, compact MIR sources.