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Wepresent a general response function formalism describing thecontribution of orientational dynamics of molecules at interfacesto spectroscopic line shapes in vibrational sum frequency generation(SFG). When reorientation occurs on the time scale comparable to vibrationaldephasing, its dynamics can be extracted from polarization-selectedSFG spectral line shapes. Unique features of orientational motionat interfaces are (1) the anisotropic case-specific equilibrium orientationaldistribution and (2) possible dynamic anisotropy (e.g., differentin-plane versus out-of-plane relaxation rates), both of which mustbe taken into account. Within the small-step rotational diffusionmodel, we present solutions for two cases, the weak-confinement model,applicable when the deviations from the isotropic case are not severe,and the wobbling-in-a-cone model, which considers a hard-wall orientingpotential. SFG line shapes are calculated for a rod-like chromophoreas a function of the rotational diffusion rate. For certain equilibriumorientational distributions, orientational dynamics may result inanomalous bi-Lorentzian line shapes (two Lorentzians of differentwidths centered and the same frequency). [ABSTRACT FROM AUTHOR]

Interactions with surfactant molecules can significantly alter the structure of interfacial water. We present a comparative study of water-surfactant interactions using two different spectroscopic approaches: water at planar surfactant monolayers by sum frequency generation (SFG) spectroscopy and interfacial water confined in reverse micelles formed by the same surfactants using IR absorption spectroscopy. We report spectral features in the OH-stretching region (3200-3700 cm-1) that are observed in both IR and SFG spectra, albeit with different relative amplitudes, for ionic surfactant sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) and nonionic surfactant polyoxyethylene(4)lauryl ether (Brij L-4) reverse micelles in hexane and the corresponding monolayers at the air/water interface. A prominent feature in the SFG spectra of the OH stretch at 3560 cm-1 is attributed to water molecules that have a weak donor hydrogen bond to the surfactant headgroup. The same feature is observed in the IR spectra of reverse micelles after deconvoluting the interfacial versus bulk spectral contributions. We performed an orientational analysis of these water molecules utilizing the polarization-dependent SFG spectra, which shows an average tilt angle of the OH stretch of surfactant-bound water molecules of ~155° with respect to the surface normal. [ABSTRACT FROM AUTHOR]