Capillary waves interface

In this brief review of dynamics in condensed phases, we have considered dense systems in various situations. First, we considered systems in equilibrium and gave an overview of how the space-time correlations, arising from the themial fluctuations of slowly varying physical variables like density, can be computed and experimentally probed. We also considered capillary waves in an inliomogeneous system with a planar interface for two cases an equilibrium system and a NESS system under a small temperature gradient. 

The fluctuations of the local interfacial position increase the effective area. This increase in area is associated with an increase of free energy Wwhich is proportional to the interfacial tension y. The free energy of a specific interface configuration u(r,) can be described by the capillary wave Hamiltonian ... 

R. Evans. The role of capillary wave fluctuations in determining the liquid-vapor interface. Analysis of the van der Waals model. Mol Phys 42 1169-1196, 1981. 

According to the capillary wave approximation , a rough interface is characterized by a width that diverges logarithmically with its transverse dimensions ... 

In the past five years, it has been demonstrated that the QELS method is a versatile technique which can provide much information on interfacial molecular dynamics [3 9]. In this review, we intend to show interfacial behavior of molecules elucidated by the QELS method. In Section II, we present the principle and the experimental apparatus of the QELS along with the historical background. The dynamic collective behavior of molecules at liquid-liquid interfaces was first obtained by improving the time resolution of the QELS method. In Section III, we show the molecular collective behavior of surfactant molecules derived from the analysis of the time courses of capillary wave frequencies. Since the... 

Capillary waves occur spontaneously at liquid surfaces or liquid liquid interfaces due to thermal fluctuations of the bulk phases. These waves have been known as surface tension waves, ripples, or ripplons for the last century, and Lamb described their properties in his book Hydrodynamics in 1932 [10]. Before that, William Thomson (Lord Kelvin) mentioned these waves in some of his many writings. 

As reviewed above, there have been many QELS studies on liquid surfaces. However, until a few years ago, reports were scarce on molecular dynamics at liquid-liquid interfaces which used time courses of capillary wave frequency. Molecular collective behavior at liquid-liquid interfaces from a QELS study was first reported by Zhang et al. in 1997 [5]. 

The incident beam normal to the interface is quasi-elastically scattered by the capillary wave with a Doppler shift at an angle determined by the following equation (Fig. 1) ... 

The capillary wave frequency is detected by an optical heterodyne technique. The laser beam, quasi-elastically scattered by the capillary wave at the liquid-liquid interface, is accompanied by a Doppler shift. The scattered beam is optically mixed with the diffracted beam from the diffraction grating to generate an optical beat in the mixed light. The beat frequency obtained here is the same as the Doppler shift, i.e., the capillary wave frequency. By selecting the order of the mixed diffracted beam, we can change the wavelength of the observed capillary wave according to Eq. (11). 

The molecular collective behavior of surfactant molecules has been analyzed using the time courses of capillary wave frequency after injection of surfactant aqueous solution onto the liquid-liquid interface [5,8]. Typical power spectra for capillary waves excited at the water-nitrobenzene interface are shown in Fig. 3 (a) without CTAB (cetyltrimethy-lammonium bromide) molecules, and (b) 10 s after the injection of CTAB solution to the water phase [5]. The peak appearing around 10-13 kHz represents the beat frequency, i.e., the capillary wave frequency. The peak of the capillary wave frequency shifts from 12.5 to 10.0kHz on the injection of CTAB solution. This is due to the decrease in interfacial tension caused by the increased number density of surfactant molecules at the interface. Time courses of capillary wave frequency after the injection of different CTAB concentrations into the aqueous phase are reproduced in Fig. 4. An anomalous temporary decrease in capillary wave frequency is observed when the CTAB solution beyond the CMC (critical micelle concentration) was injected. The capillary wave frequency decreases rapidly on injection, and after attaining its minimum value, it increases... 

FIG. 3 Power spectra for capillary waves excited at the water-nitrobenzene interface (a) without CTAB molecules and (b) 10s after injection of a CTAB solution (0.5mL, lOmM) into the water phase. 

Recently, the newly developed time-resolved quasielastic laser scattering (QELS) has been applied to follow the changes in the surface tension of the nonpolarized water nitrobenzene interface upon the injection of cetyltrimethylammonium bromide [34] and sodium dodecyl sulfate [35] around or beyond their critical micelle concentrations. As a matter of fact, the method is based on the determination of the frequency of the thermally excited capillary waves at liquid-liquid interfaces. Since the capillary wave frequency is a function of the surface tension, and the change in the surface tension reflects the ion surface concentration, the QELS method allows us to observe the dynamic changes of the ITIES, such as the formation of monolayers of various surfactants [34]. 

Dynamic surface tension has also been measured by quasielastic light scattering (QELS) from interfacial capillary waves [30]. It was shown that QELS gives the same result for the surface tension as the traditional Wilhelmy plate method down to the molecular area of 70 A. QELS has recently utilized in the study of adsorption dynamics of phospholipids on water-1,2-DCE, water-nitrobenzene and water-tetrachloromethane interfaces [31]. This technique is still in its infancy in liquid-liquid systems and its true power is to be shown in the near future. 

Recent theoretical studies indicate that thermal fluctuation of a liquid/ liquid interface plays important roles in chemical/physical properties of the surface [34-39], Thermal fluctuation of a liquid surface is characterized by the wavelength of a capillary wave (A). For a macroscopic flat liquid/liquid interface with the total length of the interface of /, capillary waves with various A < / are allowed, while in the case of a droplet, A should be smaller than 2nr (Figure 1) [40], Therefore, surface phenomena should depend on the droplet size. Besides, a pressure (AP) or chemical potential difference (An) between the droplet and surrounding solution phase increases with decreasing r as predicted by the Young-Laplace equation AP = 2y/r, where y is an interfacial tension [33], These discussions indicate clearly that characteristic behavior of chemical/physical processes in droplet/solution systems is elucidated only by direct measurements of individual droplets. 

On the other hand, a liquid/liquid interface is fluctuating thermally in the time scale of tens of picoseconds, and this induces thermal capillary waves as discussed above. Thermal capillary waves at a flat liquid/liquid interface have been studied by laser light-scattering methods, and the wavelength of the capillary wave (2) has been reported to be A 102 /im [29-31], A large... 

Analogous droplet-size dependence has been observed for electron transfer between ferrocene and hexacyanoferrate(III) across a droplet/water interface with the droplet radius of <5 /an, as described in Section III [80]. In this system, FeCp-X+ transfer is coupled with the electron transfer process and the physical properties of the droplet have been suggested to vary with r. However, droplet size effects on surface capillary waves analogous to those in the MT process may also govern the electron transfer process in the FeCp-X/Fe(IIl) system. 

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