Synthesis and novel reactivity of halomethyldimethylsulfonium salts

Iodomethyl-, chloromethyl-, and fluoromethyldimethylsulfonium salts, 4b-d, have been synthesized and are observed to be highly reactive molecules that exhibit extraordinary diversity with respect to the nature of their reactivity, undergoing facile direct substitution (S(N)2) reactions, but also being highly susceptible to electron-transfer reactions. Cyclic voltametry experiments indicated that the iodomethyldimethylsulfonium compound, 4b, is a potent electron acceptor, even surpassing the reactivity of perfluoro-n-alkyl iodides in that capacity. The iodo- and chloromethyldimethylsulfonium salts, 4b,c, as well as the analogous iodomethyltrimethylammonium salt, 3a, are shown to be reactive SET acceptors.     

Droplet formation by rapid expansion of a liquid

Molecular dynamics of two- and three-dimensional liquids undergoing a homogeneous adiabatic expansion provides a direct numerical simulation of the atomization process. The Lennard-Jones potential is used with different force cutoff distances; the cluster distributions do not depend strongly on the cutoff parameter. Expansion rates, scaled by the natural molecular time unit (about a picosecond), are investigated from unity down to 0.01; over this range the mean droplet size follows the scaling behavior of an energy balance model which minimizes the sum of kinetic plus surface energy. A second model which equates the elastic stored energy to the surface energy gives better agreement with the simulation results. The simulation results indicate that both the mean and the maximum droplet size have a power-law dependence upon the expansion rate; the exponents are -2d/3 (mean) and -d/2 (maximum), where d is the dimensionality. The mean does not show a dependence upon the system size, whereas the maximum does increase with system size, and furthermore, its exponent increases with an increase in the force cutoff distance. A mean droplet size of 2.8/eta(2), where eta is the expansion rate, describes our high-density three-dimensional simulation results, and this relation is also close to experimental results from the free-jet expansion of liquid helium. Thus, one relation spans a cluster size range from one atom to over 40 million atoms. The structure and temperature of the atomic clusters are described.     

Nanotribology of octadecyltrichlorosilane monolayers and silicon: self-mated versus unmated interfaces and local packing density effects

We use atomic force microscopy (AFM) to determine the frictional properties of nanoscale single-asperity contacts involving octadecyltrichlorosilane (OTS) monolayers and silicon. Quantitative AFM measurements in the wearless regime are performed using both uncoated and OTS-coated silicon AFM tips in contact with both uncoated and OTS-coated silicon surfaces, providing four pairs of either self-mated or unmated interfaces. Striking differences in the frictional responses of the four pairs of interfaces are found. First, lower friction occurs with OTS present on either the tip or substrate, and friction is yet lower when OTS is present on both. Second, the shape of the friction versus load plot strongly depends on whether the substrate is coated with OTS, regardless of whether the tip is coated. Uncoated substrates exhibit the common sublinear dependence, consistent with friction being directly proportional to the area of contact. However, coated substrates exhibit an unusual superlinear dependence. These results can be explained qualitatively by invoking molecular plowing as a significant contribution to the frictional behavior of OTS. Direct in situ comparison of two intrinsic OTS structural phases on the substrate is also performed. We observe frictional contrast for different local molecular packing densities of the otherwise identical molecules. The phase with lower packing density exhibits higher friction, in agreement with related previous work, but decisively observed here in single, continuous images involving the same molecules. Lateral stiffness measurements show no distinction between the two OTS structural phases, demonstrating that the difference in friction is not due to divergent stiffnesses of the two phases. Therefore, the packing density directly affects the interface's intrinsic resistance to friction, that is, the interfacial shear strength.     

Self-assembled octadecyltrichlorosilane monolayer formation on a highly hydrated silica film

A MVD silica layer that consists of a highly hydrated surface favorable for organosilane surface reaction is investigated. The MVD silica layer lacks free surface silanol groups while supporting a more extensive adsorbed water layer as compared to oxidized Si(1 0 0). Octadecyltrichlorosilane monolayers (OTS) deposited on the MVD silica layer are found to follow the same mechanisms of growth and exhibit properties comparable to those formed on oxidized Si(1 0 0) surfaces. The growth process of octadecylsiloxane films is investigated as a function of immersion time and temperature by utilizing ATR-FTIR, ellipsometry, contact angle analysis, and AFM. The MVD silica layer is shown to support an ordered interfacial water structure that is more tightly bound due to a higher degree of hydrogen bonding associated with the hydroxylated surface. The importance of interfacial water on the OTS film formation process is highlighted and the role of free OH groups on the adsorption mechanism is diminished. It is shown that OTS films can be formed on a highly hydrated surface comparable to those formed on oxidized Si(1 0 0) surfaces.     

Experimental requirement of the error-compensating five-frame interferogram-collecting sequence used in phase-shifting interferometry

Digital phase-shifting interferometry (PSI), a technique widely used in optical testing, requires interferograms collected at optical phase differences separated by a definite phase step. The five-frame interferogram-collecting sequence suggested by Hariharan et al. [Appl. Opt. 26, 2504 (1987)] is extremely effective in significantly reducing the errors in height profiles derived using PSI that are caused by phase-step errors. In this Letter, we report on a class of five-frame sequence that, owing to its mathematical equivalence with the one suggested by Hariharan et al. and its ease of execution, is more commonly used but is much less effective in reducing the height profile errors caused by phase-step errors.     

Investigation of a vapor-deposited thin silica film: morphological and spectral characterization

Surface modification reactions by organosilicon compounds have demonstrated great success in a wide variety of applications. However, they are of limited usefulness in that they only proceed appreciably on surfaces that have an abundance of reactive hydroxyl groups, thus preventing their application to some materials of technological relevance, such as plastics and polymers. A process capable of depositing a surface rich in reactive hydroxyl groups onto a wide variety of substrates could potentially enable the extension of organosilane surface modification reactions to new materials, but conventional processes for depositing oxide layers require temperatures that are too high for most polymers and plastics. It has been shown that silica layers can be deposited from the vapor-phase hydrolysis of tetrachlorosilane at room temperature, but little if any work has been done to characterize the resulting films. In this work, ellipsometry, atomic force microscopy, and Fourier transform infrared spectroscopy are employed to study the characteristics of films formed from this process. Interestingly, very different film morphologies can be obtained by changing key processing parameters. Furthermore, isotopic exchange experiments and dehydration studies show that the surfaces of the silica films obtained by this method are composed entirely of hydrogen-bonded silanol groups and do not exhibit any freely vibrating surface silanol groups, a result that is in contrast with conventionally prepared silica materials. Still, this layer has been shown to behave very similarly to conventional silica materials with respect to surface reactions. Finally, infrared spectral data and contact angle data demonstrate that this method can be employed to deposit silica layers onto poly(methyl methacrylate) and polystyrene surfaces.     

A modulated lamp system for solar UV-B (280--320 nm). Supplementation studies in the field

Precise control and modulation of fluorescent sunlamps are necessary for ecologically valid simulation of solar UV-B (280-320 nm) radiation enhancement which would correspond to ozone reduction. A control system is described which allows lamp emittance to be modulated over a large dynamic range (50:1), permits stable lamp operation and starting at low temperatures, and provides a sensitive feedback loop to compensate for both atmospheric conditions, such as cloud cover, as well as changes in radiant emittance from the lamps resulting from factors such as temperature and lamp age.     

The single-mode rate equations for semiconductor lasers with thermal effects

A mathematical model describing the coupling of electrical,optical and thermal effects in semiconductor lasers is introduced.Numerical and asymptotic solutions are derived, including expressionsfor key physical quantities such as the initial time delay,the frequency of spike oscillation and the temperature rise,together with its influence on the photon density, the electronconcentration and the threshold current. The consequences ofthermal effects in reducing efficiency are thus quantified.