Applications

Sum-frequency generation (SFG) spectroscopy is used to assess the vibrational properties of surfaces and interfaces with a monolayer sensitivity. Unlike Raman spectroscopy that is sensitive to the bulk properties, SFG spectroscopy is exquisitely sensitive to the physical and chemical properties of molecular layers at surfaces and interfaces where inversion symmetry is broken.

In SFG spectroscopy, a mid-IR beam is sent onto the surface or interface where it is overlapped with a visible beam. The specific properties of the resulting sum-frequency signal, such as polarization and intensity, provide information on dipole orientation and vibrational spectra at the surface. SFG is a second-order nonlinear process and is allowed only when inversion symmetry is broken, making it a specifically surface-sensitive method. In this type of spectroscopy, one of the pulses is required to have a sufficiently narrow spectral bandwidth in order to obtain a high spectral resolution and, subsequently, distinguish the vibrational fingerprints of the investigated molecules.

One of the main scientific targets of SFG spectroscopy is studying the dynamics of interfacial water, which is done by observing the OH stretching vibrations of normal water and OD stretching vibrations of heavy water at 2.6 – 3.5 μm and 3.5 – 4.5 μm, respectively. Other spectral ranges of interest are 4.5 – 5.5 μm, where the vibrations of metal carbonyls and nitriles occur, and 5.5 – 6.5 μm, where molecular vibrations of interfacial biomolecules take place. Moreover, going further into the mid-IR is also of high interest due to lower frequency biomolecular vibrations.

Broadband mid-IR source such as ORPHEUS-MIR, pumped by PHAROS or CARBIDE laser, covers the spectral ranges of interest and addresses many vibrational levels at once, while SHBC is used to double the laser frequency and narrow down the spectral bandwidth to match the aforementioned requirements. In this configuration, the SFG signal is generated in the visible spectral range, eliminating the need for complex infrared detection.