Second-order nonlinear spectroscopy has proven to be a powerful tool in elucidating key chemical and structural characteristics at a variety of interfaces. However, the presence of interfacial potentials may lead to complications regarding the interpretation of second harmonic and vibrational sum frequency generation responses from charged interfaces due to mixing of absorptive and dispersive contributions. Here, we examine by means of mathematical modeling how this interaction influences second-order spectral lineshapes. We discuss our findings in the context of reported nonlinear optical spectra obtained from charged water/air and solid/liquid interfaces and demonstrate the importance of accounting for the interfacial potential-dependent χ (3) term in interpreting lineshapes when seeking molecular information from charged interfaces using second-order spectroscopy.

Probing the polarization of water molecules at charged interfaces by second harmonic generation spectroscopy has been heretofore limited to isotropic materials. Here we report non-resonant nonlinear optical measurements at the interface of anisotropic z-cut α-quartz and water under conditions of dynamically changing ionic strength and bulk solution pH. We find that the product of the third-order susceptibility and the interfacial potential, χ(3) × Φ(0), is given by (χ1(3)−iχ2(3)) × Φ(0), and that the interference between this product and the second-order susceptibility of bulk quartz depends on the rotation angle of α-quartz around the z axis. Our experiments show that this newly identified term, iχ(3) × Φ(0), which is out of phase from the surface terms, is of bulk origin. The possibility of internally phase referencing the interfacial response for the interfacial orientation analysis of species or materials in contact with α-quartz is discussed along with the implications for conditions of resonance enhancement.

We report ionic strength-dependent phase shifts in second harmonic generation (SHG) signals from charged interfaces that verify a recent model in which dispersion between the fundamental and second harmonic beams modulates observed signal intensities. We show how phase information can be used to unambiguously separate the χ (2) and interfacial potential-dependent χ (3) terms that contribute to the total signal and provide a path to test primitive ion models and mean field theories for the electrical double layer with experiments to which theory must conform. Finally, we demonstrate the new method on supported lipid bilayers and comment on the ability of our new instrument to identify hyper-Rayleigh scattering contributions to common homodyne SHG measurements in reflection geometries.

We explore by means of modeling how absorptive-dispersive mixing between the second- and third-order terms modifies the imaginary χ responses from air/water interfaces under conditions of varying charge densities and ionic strength. To do so, we use published Im(χ) and χ spectra of the neat air/water interface that were obtained either from computations or experiments. We find that the χ spectral lineshapes corresponding to experimentally measured spectra contain significant contributions from both interfacial χ and bulk χ terms at interfacial charge densities equivalent to less than 0.005% of a monolayer of water molecules, especially in the 3100 to 3300 cm frequency region. Additionally, the role of short-range static dipole potentials is examined under conditions mimicking brine. Our results indicate that surface potentials, if indeed present at the air/water interface, manifest themselves spectroscopically in the tightly bonded H-bond network observable in the 3200 cm frequency range.

Second harmonic generation (SHG) spectroscopy has been applied to probe the fused silica/water interface at pH 7 and the uncharged 11¯02 sapphire/water interface at pH 5.2 in contact with aqueous solutions of NaCl, NaBr, NaI, KCl, RbCl, and CsCl as low as several 10 μM. For ionic strengths up to about 0.1 mM, the SHG responses were observed to increase, reversibly for all salts surveyed, when compared to the condition of zero salt added. Further increases in the salt concentration led to monotonic decreases in the SHG response. The SHG increases followed by decreases are found to be consistent with recent reports of phase interference and phase matching in nonlinear optics. By varying the relative permittivity employed in common mean field theories used to describe electrical double layers and by comparing our results to available literature data, we find that models recapitulating the experimental observations are the ones in which (1) the relative permittivity of the diffuse layer is that of bulk water, with other possible values as low as 30, (2) the surface charge density varies with salt concentration, and (3) the charge in the Stern layer or its thickness varies with salt concentration. We also note that the experimental data exhibit sensitivity depending on whether the salt concentration is increased from low to high values or decreased from high to low values, which, however, is not borne out in the fits, at least within the current uncertainties associated with the model point estimates.