Heterodyne-Detected Second Harmonic Generation Research Articles

In Situ Heterodyne-Detected Second-Harmonic Generation Study of the Influence of Cholesterol on Dye Molecule Adsorption on Lipid Membrane.

Cholesterol plays an essential role in regulating the functionality of biomembranes. This study employed in situ second-harmonic generation (SHG) to investigate the adsorption behavior of the dye molecule 4-(4-(diethylamino)styryl)-N-methyl-pyridinium iodide (D289) on a biomimic membrane composed of 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (sodium salt) (DPPG) and cholesterol. The time-dependent polarization SHG intensity exhibited an initial rapid increase, followed by a subsequent decline. The initial increased SHG intensity is responsible for the electrostatic interaction-driven adsorption of D289 onto the membrane, while the decrease in the SHG signal results from the broadening of the orientation distribution within the membrane. Heterodyne-detected SHG (HD-SHG) measurements demonstrated that the adsorption of dye molecules influenced the phase of the induced electric field. The interfacial potential Φ(0) as a function of time was measured, and we found that even after reaching a stable Stern layer state, the diffusion layer continued to exhibit a dynamic change. This study offers a comprehensive understanding of the influence of cholesterol on adsorption, reorientation dynamics, and dynamic changes in the reorientation of water in the diffusion layer.

Probing the adsorption configuration of methanol at a charged air/aqueous interface using nonlinear spectroscopy.

Investigating the effects of electrolyte ions on the adsorption configuration of methanol at a charged interface is important for studying the interface structure of electrolyte solutions and the oxidation mechanism of methanol in fuel cells. This study uses sum frequency generation (SFG) and heterodyne-detected second harmonic generation (HD-SHG) to investigate the adsorption configuration of methanol at the air/aqueous interface of 0.1 M NaClO4 solution, 0.1 M HClO4 solution and pure water. The results elucidate that the ion effect in the electrolyte solution affects the interface's charged state and the methanol's adsorption conformation at the interface. The negatively charged surface of the 0.1 M NaClO4 solution and the positively charged surface of the 0.1 M HClO4 solution arise from the corresponding specific ionic effects of the electrolyte solution. The orientation angle of methyl with respect to the surface normal is 43.4° ± 0.1° at the 0.1 M NaClO4 solution surface and 21.5° ± 0.2° at the 0.1 M HClO4 solution surface. Examining these adsorption configurations in detail, we find that at the negatively charged surface the inclined orientation angle (43.4°) of methanol favors the hydroxymethyl production by breaking the C-H bond, while at the positively charged surface the upright orientation angle (21.5°) of methanol promotes the methoxy formation by breaking the O-H bond. These findings not only illuminate the intricate ion effects on small organic molecules but also contribute to a molecular-level comprehension of the oxidation mechanism of methanol at electrode interfaces.

Quantification of Stern Layer Water Molecules, Total Potentials, and Energy Densities at Fused Silica:Water Interfaces for Adsorbed Alkali Chlorides, CTAB, PFOA, and PFAS.

We have employed amplitude- and phase-resolved second-harmonic generation spectroscopy to investigate ion-specific effects of monovalent cations at the fused silica:water interface maintained under acidic, neutral, and alkaline conditions. We find a negligible dependence of the total potential (as negative as -400 mV at pH 14), the second-order nonlinear susceptibility (as large as 1.5 × 10-21 m2 V-1 at pH 14), the number of Stern layer water molecules (1 × 1015 cm-2 at pH 5.8), and the energy associated with water alignment upon going from neutral to high pH (ca. -24 kJ mol-1 to -48 kJ mol-1 at pH 13 and 14, close to the cohesive energy of liquid water but smaller than that of ice) on chlorides of the alkali series (M+ = Li+, Na+, K+, Rb+, and Cs+). Attempts are presented to provide estimates for the molecular hyperpolarizability of the cations and anions in the Stern layer at high pH, which arrive at ca. 20-fold larger values for αtotalions(2) = αM+(2) + αOH-(2) + αCl-(2) when compared to water's molecular hyperpolarizability estimate from theory and point to a sizable contribution of deprotonated silanol groups at high pH. In contrast to the alkali series, a pronounced dependence of the total potential and the second-order nonlinear susceptibility on monovalent cationic (cetrimonium bromide, CTAB) and anionic (perfluorooctanoic and perfluorooctanesulfonic acid, PFOA and PFOS) surfactants was quantifiable. Our findings are consistent with a low surface coverage of the alkali cations and a high surface coverage of the surfactants. Moreover, they underscore the important contribution of Stern layer water molecules to the total potential and second-order nonlinear susceptibility. Finally, they demonstrate the applicability of heterodyne-detected second-harmonic generation spectroscopy for identifying perfluorinated acids at mineral:water interfaces.

Phase-Modulated Degenerate Parametric Amplification Microscopy

Second-order nonlinear optical interactions, including second-harmonic generation (SHG) and sum-frequency generation (SFG), can reveal a wealth of information about chemical, electronic, and vibrational dynamics at the nanoscale. Here, we demonstrate a powerful and flexible new approach, called phase-modulated degenerate parametric amplification (DPA). The technique, which allows for facile retrieval of both the amplitude and phase of the second-order nonlinear optical response, has many advantages over conventional or heterodyne-detected SHG, including the flexibility to detect the signal at either the second harmonic or fundamental field wavelength. We demonstrate the capabilities of this approach by imaging multigrain flakes of single-layer MoS2. We identify the absolute crystal orientation of each MoS2 domain and resolve grain boundaries with high signal contrast and sub-diffraction-limited spatial resolution. This robust all-optical method can be used to characterize structure and dynamics in organic and inorganic systems, including biological tissue, soft materials, and metal and semiconductor nanostructures, and is particularly well-suited for imaging in media that are absorptive or highly scattering to visible and ultraviolet light.