RESUMEN

Polymer nanostructures were directly written onto substrates in ultra-high vacuum. The polymer ink was coated onto atomic force microscope (AFM) probes that could be heated to control the ink viscosity. Then, the ink-coated probes were placed into an ultra-high vacuum (UHV) AFM and used to write polymer nanostructures on surfaces, including surfaces cleaned in UHV. Controlling the writing speed of the tip enabled the control over the number of monolayers of the polymer ink deposited on the surface from a single to tens of monolayers, with higher writing speeds generating thinner polymer nanostructures. Deposition onto silicon oxide-terminated substrates led to polymer chains standing upright on the surface, whereas deposition onto vacuum reconstructed silicon yielded polymer chains aligned along the surface.

RESUMEN

The structure and growth of thin films of aniline vapor deposited on Ag(111) and Ag(110) surfaces have been examined using optical second harmonic generation (SHG) and linear optical differential reflectivity (DR). Aniline thin films deposited at 90 K give a detectable SH signal that arises from small polycrystallites with orientation anisotropy in the film. Upon annealing, the SH signal decreases, first due to premelting (at approximately 145 K) of the polycrystallites and then sublimation (at approximately 180 K) of the film. Quantitative analysis of the SH intensity change by a premelting model [J. Phys. Chem. 1988, 92, 7241] allows the determination of the average size of the crystallites as 1.1 nm in diameter and containing approximately 45 aniline molecules. The existence of the nanocrystalline structure and its premelting are confirmed by DR experiments. The DR signal around 145 K exhibits change corresponding to an order-disorder transition. Quantitative analysis of the DR data results in the same nanocrystallite size. Experimental observations indicate that films deposited at 90 K contain not only nanocrystallites but also approximately 30% porosity, which can be reduced by annealing. At temperatures above 195 K, micron-size crystallites start to form within the amorphous film, causing a large amount of light scattering while the film sublimates. It appears that, for molecules such as aniline with stronger intermolecular interactions, more enthalpy is released, upon adsorption to the local surrounding molecules, causing them to reorient into crystalline form. The low deposition temperature, on the other hand, prevents diffusion for further crystallization beyond nanocrystallites. The refractive index of the amorphous aniline solid can be determined as 1.68 +/- 0.03.

RESUMEN

The adsorption of monolayer and multilayer benzene on the Ag(111) surface was characterized using temperature programmed desorption (TPD). TPD spectra revealed two broad peaks at approximately 205 and approximately 150 K at submonolayer coverage and a sharper, multilayer peak at 140 K. Analysis of the coverage-dependent shape and shift of the two submonolayer peaks has resulted in their assignment to desorption from two different binding geometries on threefold-hollow sites with symmetries C(3v)(sigma d) and C(3v)(sigma v). The TPD peak analysis incorporated inter-adsorbate repulsive interaction that resulted from the local dipole moment at the adsorption site induced by the adsorbate-surface charge transfer bonding. The analysis has yielded desorption energies of 54.9 +/- 0.8 and 50.4 +/- 0.4 kJ/mol for the C(3v)(sigma d) and C(3v)(sigma v) configurations, respectively. The interface dipole and polarizability of the benzene-silver complex have been determined to be 5.4 +/- 1.8 D and 14 +/- 10 A3, respectively. Repulsive interactions in the monolayer were found to lower the desorption energy from the zero-coverage value by 14.8 kJ/mol. Leading edge analysis of the multilayer peak yielded a desorption energy of 40.9 +/- 0.7 kJ/mol.

RESUMEN

Polymer nanostructures composed of poly(3-dodecylthiophene) (PDDT) have been directly written with control of polymer strand alignment and monolayer-by-monolayer thickness down to a single molecular monolayer (2.6 nm). The molecularly ordered nanostructures were written on silicon oxide surfaces using thermal dip-pen nanolithography, where an atomic force microscope cantilever with integrated tip heater was precoated with solid PDDT. The PDDT was precisely deposited onto the surface when the tip temperature was set close to PDDT's melting temperature.

RESUMEN

The isothermal adsorption and desorption of monolayer water on a Ag(110) surface in the temperature range of 130-137 K were characterized by monitoring second-harmonic (SH) generation from the silver surface. The SH intensity resonantly enhanced by the silver surface-state transition is highly sensitive to the amount of silver surface area covered by water and allows the observation of an abrupt change in the adsorption/desorption behavior at 133.5 K. At temperatures below 133.5 K water wets the Ag surface in a two-dimensional structure with a measured desorption energy of 25.0 (+/-3.3) kJ/mol. At temperatures greater than 133.5 K water desorbs from three-dimensional clusters with a measured desorption energy of 48.3 (+/-2.2) kJ/mol, in agreement with temperature-programmed desorption measurements. This wetting-dewetting transition of water adsorbed on the silver surface at 133.5 K is supported by classical nucleation theory calculations.

RESUMEN

The adsorption geometries and surface reactions of various C(6) hydrocarbons (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) adsorbed on Pt(111) were investigated using sum frequency generation (SFG) surface vibrational spectroscopy. The adsorptions and reactions were carried out in 1.5 Torr of C(6) hydrocarbons in the absence and presence of excess hydrogen (15 Torr) and in the temperature range 296-453 K. At 296 K and in the presence of excess hydrogen, n-hexane and 3-methylpentane adsorbed molecularly on Pt(111) mostly in "flat-lying" geometries. Upon heating the sample up to 453 K, the molecules underwent dehydrogenation to form new surface species in "standing-up" geometries, such as hexylidyne and metallacyclic species. However, 2-methylpentane and 1-hexene were dehydrogenated to metallacyclobutane and hexylidyne, respectively, at 296 K in the presence of excess hydrogen. The dehydrogenated species remained unreacted on the surface upon heating the sample up to 453 K. The absence of excess hydrogen enhanced dehydrogenation of n-hexane and 3-methylpentane to form pi-allyl c-C(6)H(9) and metallacyclohexane, respectively, at 296 K. Upon heating to 453 K, the pi-allyl c-C(6)H(9) species underwent irreversible dehydrogenation, while hexylidyne and metallacyclic species remained unreacted. On the basis of these results, the mechanisms for catalytic isomerization and dehydrocyclization of n-hexane, which are the important "reforming" reactions to produce high-octane fuels over platinum, were discussed.

Asunto(s)

RESUMEN

It is demonstrated that by using optical second harmonic generation the orientation and alignment of molecules in the interfacial layer between two solids, a thin solid molecular film and a metal substrate, can be determined. The pyridine molecules in the interfacial layer underneath the film are found to align along the [110] direction of the Ag(110) surface with a small tilt angle (approximately 11 degrees) from the surface normal. This interfacial ordering is found to have a notable effect in inducing crystallization at the heterogeneous boundary of the amorphous molecular film.

Asunto(s)

RESUMEN

Sum frequency generation (SFG) surface vibrational spectroscopy has been used to identify reactive surface intermediates in situ during catalytic dehydrogenation reactions of high-pressure cyclohexane (C(6)H(12)) on the Pt(111) crystal surface in the presence and absence of high-pressure hydrogen. These experiments provide the first spectroscopic evidence of cyclohexyl (C(6)H(11)) as a reactive surface intermediate during the cyclohexane catalytic conversion to benzene at high pressure in the presence of excess hydrogen. In addition, it was proposed from temperature-dependent SFG experiments that dehydrogenation of cyclohexyl is a rate-limiting step in the cyclohexane catalytic conversion to benzene.