The activities of surfactant ions (aD) and counterions (aNa) were directly obtained by the EMF measurement of a concentration cell with an ion-exchange membrane and by pNa measurements respectively for aqueous solutions of sodium dodecyl sulfate (NaDS) below and above the CMC. The mean activity and activity coefficient were also calculated. From these data, together with the surface tension (γ) measured by the Wilhelmy method and the amount of adsorption (Γ) measured by the radiotracer method, the following results were obtained: (1) Mean activity was not constant, but increased with the concentration above the CMC. (2) The Gibbs adsorption isotherm was directly verified from the aD and aNa vs. concentration relations. (3) The decrease in γ observed above the CMC was in agreement with that calculated from the activity data. (4) The logaD vs. logaNa plots above the CMC showed a linear relation, indicating the validity of the charged phase separation model as the mechanism of micelle formation. The degree of the counterion attachment of the micelles was found to be 0.73 up to about 80 mmol/l. (5) The intermicellar concentrations of Na+ and DS− ions were calculated; the former increases, while the latter decreases with the concentration. (6) The product of the concentration with an osmotic coefficient was linear with the concentration above the CMC, tangent of the slope being about 0.7.
We carried out direct measurement of adsorbed amount at the air-solution interface to confirm the validity of the Gibbs adsorption equation by using radiochemically and surface chemically pure tritiated sodium dodecylsulfate (TSDS) and a sheet scintillation counter, which was developed for the purpose of counting β-rays of tritium in air. The adsorbed amount increased with increasing SDS concentration and showed the saturation values of 3.19×10−10 mol/cm2 in the concentration region from 3.2×10−3 to 14.4×10−3 mol/1000 g solution at 25°C. For the salt-free solution of ionic surfactant the Gibbs adsorption equation is confirmed to be valid for n=2 when activity in place of concentration is used. The equation of state for the ionic adsorbed film is further proposed. The cohesive pressure due to the attraction between hydrocarbon chains was given as a function of inverse molecular area.
We study the effect of dynamical tunneling on emission from ray-chaotic microcavities by introducing a suitably designed deformed disk cavity. We focus on its high quality factor modes strongly localized along a stable periodic ray orbit confined by total internal reflection. It is shown that dominant emission originates from the tunneling from the periodic ray orbit to chaotic ones; the latter eventually escape from the cavity refractively, resulting in directional emission that is unexpected from the geometry of the periodic orbit, but fully explained by unstable manifolds of chaotic ray dynamics. Experimentally performing selective excitation of those modes, we succeeded in observing the directional emission in good agreement with theoretical prediction. This provides decisive experimental evidence of dynamical tunneling in a ray-chaotic microcavity.
The limaçon-shaped semiconductor microcavity is a ray-chaotic cavity sustaining low-loss modes with mostly unidirectional emission patterns. Investigating these modes systematically, we show that the modes correspond to ray description collectively, rather than individually. In addition, we present experimental data on multimode lasing emission patterns that show high unidirectionality and closely agree with the ray description. The origin of this agreement is well explained by the collective correspondence mechanism.
The phonon modes of molecular crystals in the terahertz frequency region often feature delicately coupled inter- and intra-molecular vibrations. Recent advances in density functional theory such as DFT-D(*) have enabled accurate frequency calculation. However, the nature of normal modes has not been quantitatively discussed against experimental criteria such as isotope shift (IS) and correlation field splitting (CFS). Here, we report an analytical mode-decoupling method that allows for the decomposition of a normal mode of interest into intermolecular translation, libration, and intramolecular vibrational motions. We show an application of this method using the crystalline anthracene system as an example. The relationship between the experimentally obtained IS and the IS obtained by PBE-D(*) simulation indicates that two distinctive regions exist. Region I is associated with a pure intermolecular translation, whereas region II features coupled intramolecular vibrations that are further coupled by a weak intermolecular translation. We find that the PBE-D(*) data show excellent agreement with the experimental data in terms of IS and CFS in region II; however, PBE-D(*) produces significant deviations in IS in region I where strong coupling between inter- and intra-molecular vibrations contributes to normal modes. The result of this analysis is expected to facilitate future improvement of DFT-D(*).
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