Temperature Dependence of the Structure of Langmuir Films of Normal-Alkanes on Liquid Mercury

The temperature dependent phase behavior of Langmuir films of n-alkanes [CH3(CH2)n−2CH3, denote Cn] on mercury was studied for chain lengths 19 ⩽ n ⩽ 22 and temperatures 15 ⩽ T ⩽ 44 °C, using surface tensiometry and surface x-ray diffraction methods. In contrast with Langmuir films on water, where molecules invariably orient roughly surface normal, alkanes on mercury are always oriented surface parallel and show no long-range in-plane order at any surface pressure. A gas and several condensed phases of single, double, and triple layers of lying-down molecules are found, depending on n and T. At high coverages, the alkanes studied here show transitions from a triple to a double to a single layer with increasing temperature. The transition temperature from a double to a single layer is found to be ∼ 5 °C, lower than the bulk rotator-to-liquid melting temperature, while the transition from a triple to a double layer is about as much below the double-to-single layer transition. Both monolayer and bulk transition temperatures show a linear increase with n with identical slopes of ∼ 4.5 °C/CH2 within the range of n values addressed here. It is suggested that the film and bulk transitions are both driven by a common cause: the proliferation of gauche defects in the chain with increasing temperature.Engineering and Applied Science

Competition between Surface Layering and Surface Phase Formation in Dilute Liquid Hg−Au Alloys

We present temperature-dependent X-ray reflectivity measurements of liquid Hg alloyed with 0.06−0.20 atom % Au. At low Au concentrations, we find temperature-dependent surface-induced layering similar to that observed in pure Hg, except that the presence of Au reduces the layering amplitude. Upon approaching the solubility limit of Au in Hg, a new surface phase forms which is 1−2 atomic diameters thick and has a density of about half that of bulk Hg. We present a surface phase diagram, summarizing the evolution of this unexpected surface structure upon varying composition and temperature. Such surface modifications may account for the variations observed in catalytic and electrochemical reactions at liquid metal surfaces upon alloying.Engineering and Applied Science

Langmuir Films of Normal-Alkanes on the Surface of Liquid Mercury

The coverage dependent phase behavior of molecular films of n-alkanes ($CH_{3}CH_{n−2}CH_3$, denote Cn) on mercury was studied for lengths 10 $\leq$ n $\leq$ 50, using surface tensiometry and surface x-ray diffraction methods. In contrast with Langmuir films on water, where roughly surface-normal molecular orientation is invariably found, alkanes on mercury are always oriented surface-parallel, and show no long-range in-plane order at any surface pressure. At a low coverage a two-dimensional gas phase is found, followed, upon increasing the coverage, by a single condensed layer (n $\leq$ 18), a sequence of single and double layers (19 $\leq$ n $\leq$ 20; n $\geq$ 26), or a sequence of single, double, and triple layers (22 $\leq$ n $\leq$ 24). The thermodynamical and structural properties of these layers, as determined from the measurements, are discussed.Engineering and Applied Science

Surface Induced Order in Liquid Metals and Binary Alloys

Measurements of the surface x-ray scattering from several pure liquid metals (Hg, Ga, and In) and from three alloys (Ga-Bi, Bi-In, and K-Na) with different heteroatomic chemical interactions in the bulk phase are reviewed. Surface-induced layering is found for each elemental liquid metal. The surface structure of the K-Na alloy resembles that of an elemental liquid metal. Bi-In displays pair formation at the surface. Surface segregation and a wetting film are found for Ga-Bi.Comment: 10 pages, 3 fig, published in Journal of Physics: Condensed Matte

Dynamics of 8CB confined into porous silicon probed by incoherent neutron backscattering experiments

Confinement in the nanochannels of porous silicon strongly affects the phase behavior of the archetype liquid-crystal 4-n-octyl-4-cyanobiphenyl (8CB). A very striking phenom- enon is the development of a short-range smectic order, which occurs on a very broad temperature range. It suggests in this case that quenched disorder effects add to usual finite size and surface interaction effects. We have monitored the temperature variation of the molecular dynamics of the confined fluid by incoherent quasielastic neutron scat- tering. A strongly reduced mobility is observed at the highest temperatures in the liquid phase, which suggests that the interfacial molecular dynamics is strongly hindered. A continuously increasing slowdown appears on cooling together with a progressive growth of the static correlation lengt

Wetting Behavior at the Free Surface of a Liquid Gallium–Bismuth Alloy: An X-ray Reflectivity Study Close to the Bulk Monotectic Point

We present X-ray reflectivity measurements from the free surface of a liquid gallium–bismuth alloy (Ga–Bi) in the temperature range close to the bulk monotectic temperature $T_{mono}$=222$^\circ$C. Our measurements indicate a continuous formation of a thick wetting film at the free surface of the binary system driven by the first order transition in the bulk at the monotectic point. We show that the behavior observed is that of a complete wetting at a tetra point of solid–liquid–liquid–vapor coexistence.Engineering and Applied Science

Surface Layering in Liquid Gallium: An X-Ray Reflectivity Study

Surface-induced atomic layering in liquid gallium has been observed using x-ray reflectivity, ultrahigh vacuum conditions, and sputtered clean surfaces. Reflectivity data, collected on a supercooled liquid sample to momentum transfers as large as $q_z$ = 3.0 Å$^{-1}$, exhibit a strong maximum near 2.4 Å$^{-1}$ indicating a layer spacing that is comparable to its atomic dimensions. The amplitude of the electron density oscillations decays with a characteristic length of 6 Å. This is unexpectedly twice that of recent results for Hg, and the difference may be related to covalent bonding or supercooling.Engineering and Applied Science

Surface Structure of Liquid Metals and the Effect of Capillary Waves: X-ray Studies on Liquid Indium

We report x-ray reflectivity (XR) and small angle off-specular diffuse scattering (DS) measurements from the surface of liquid Indium close to its melting point of $156^\circ$C. From the XR measurements we extract the surface structure factor convolved with fluctuations in the height of the liquid surface. We present a model to describe DS that takes into account the surface structure factor, thermally excited capillary waves and the experimental resolution. The experimentally determined DS follows this model with no adjustable parameters, allowing the surface structure factor to be deconvolved from the thermally excited height fluctuations. The resulting local electron density profile displays exponentially decaying surface induced layering similar to that previously reported for Ga and Hg. We compare the details of the local electron density profiles of liquid In, which is a nearly free electron metal, and liquid Ga, which is considerably more covalent and shows directional bonding in the melt. The oscillatory density profiles have comparable amplitudes in both metals, but surface layering decays over a length scale of $3.5\pm 0.6$ \AA for In and $5.5\pm 0.4$ \AA for Ga. Upon controlled exposure to oxygen, no oxide monolayer is formed on the liquid In surface, unlike the passivating film formed on liquid Gallium.Comment: 9 pages, 5 figures; submitted to Phys. Rev.

Incommensurate Smectic Order at the Free Surface in the Nematic Phase of 4−N−Heptylphenyl−4′−(4"−Nitrobenzoyloxy)Benzoate(DB7NO2)4-N-Heptylphenyl-4'-(4"-Nitrobenzoyloxy)Benzoate (DB7NO_2)

We report x-ray reflectivity measurements on the free surface of $4-n-heptylphenyl-4'-(4"-nitrobenzoyloxy)benzoate (DB7NO_2)$ at the nematic to smectic-A phase transition, $T_{NA}=99.9^{\circ}C$. The free surface in the nematic phase exhibits smecticlike ordering at two q vectors, one which is commensurate with the smectic-A monolayer q vector $q_2$. The other q vector is incommensurate corresponding to ordering at $\sim 0.59q_2$. The commensurate peak constructively interferes with the air-liquid interface while the incommensurate peak destructively interferes. These results are compared with bulk-phase x-ray scattering measurements.Engineering and Applied Science

Integrated X-Ray-Scattering Intensity Measurement of the Order Parameter at the Nematic-to-Smectic-A Phase Transition

The temperature dependence of the square of the smectic order parameter, $\mid \psi \mid^2$, was determined from the integrated x-ray scattering intensity. The data are described very well by the form $I(t)/I(0)=1 \mp A^{(\pm)}\mid t \mid^x$, where $t=(T-T_{NA})/T_{NA}$. The determined values for x do not agree with the theoretically expected value $x=1-\alpha$, where $\alpha$ is the heat-capacity exponent. This disagreement raises questions concerning the quantitative validity of the Landau–de Gennes free energy.Engineering and Applied Science