Lyman-α driven molecule formation on SiO2 surfaces-connection to astrochemistry on dust grains in the interstellar medium.

As a model for silicate dust grains in the interstellar medium, we have used high area amorphous SiO(2) as a surface on which to carry out Lyman-α (10.2 eV) photodecomposition of adsorbed N(2)O at 71 K and at a coverage of ∼0.3 monolayer. The N(2)O molecules are adsorbed by hydrogen bonding to surface Si-OH groups. Transmission IR spectroscopy measurements permit the observation of the consumption of adsorbed N(2)O and the production of various photoproducts. It is observed that in comparison to N(2)O consumption, the relative rate of formation of the products NO(2) and N(2)O(4) made by combination reactions is enhanced significantly on the SiO(2) surface. Reactions between photogenerated radicals themselves or between radicals and parent N(2)O on the SiO(2) surface exceed the relative rates observed in the gas phase by factors of up to ∼20. As the complexity of the combination product increases, its relative production rate, compared to the gas phase, increases due to the involvement of multiple surface-combination elementary steps. It is proposed that the enhancement of combination reactions on the SiO(2) surface is due to the surface's ability to absorb excess energy evolved during the chemical-bond-forming events on the surface. This principle is probably significant on grain surfaces supporting photochemical processes of astrochemical interest, and indeed is expected. The cross section for adsorbed N(2)O photodecomposition on the porous SiO(2) surface is about 7 × 10(-20) cm(2) and the quantum yield for the adsorbed molecule decomposition is about 0.006, compared to a quantum yield of 1.46 in the gas phase. This decrease in photon efficiency is attributed to absorption and scattering of Lyman-α radiation by the SiO(2) particles.

The role of gold adatoms and stereochemistry in self-assembly of methylthiolate on Au(111).

On the basis of high resolution STM images and DFT modeling, we have resolved low- and high-coverage structures of methylthiolate (CH(3)S) self-assembled on the Au(111) surface. The key new finding is that the building block of all these structures has the same stoichiometry of two thiolate species joined by a gold adatom. The self-arrangement of the methylthiolate-adatom complexes on the surface depends critically on their stereochemical properties. Variations of the latter can produce local ordering of adatom complexes with either (3 x 4) or (3 x 4 square root(3)) periodicity. A possible structural connection between the (3 x 4 square root(3)) structure and commonly observed (square root(3) x square root(3))R30 degrees phase in methylthiolate self-assembled monolayers is developed by taking into account the reduction in the long-range order and stereochemical isomerization at high coverage. We also suggest how the observed self-arrangements of methylthiolate may be related to the c(4 x 2) phase of its longer homologues.

Role of conformation in the electronic properties of chemisorbed pyridine on Cu(110): an STM/STS study.

Pyridine was chemisorbed on Cu(110) at 10 K and observed using STM at 5 K as dosed and after annealing to temperatures between 20 and 300 K. At very low coverage, two molecular species with different apparent heights are observed to coexist. The higher species is assigned to a pyridine molecule bonded with its symmetry axis perpendicular to the surface plane, while the lower species is assigned to a pyridine molecule that is tilted down toward the surface plane. At low coverage, the tilted pyridine species predominates on the surface, but as the total surface coverage of pyridine increases, the molecules stand up until the upright geometry becomes favored. Measurements of the STS of the two species show different molecular resonances derived from the lowest unoccupied pyridine pi* orbitals. The tilted pyridine species has a peak in the unoccupied local density of states at 2.6 +/- 0.1 eV, whereas the upright pyridine species has a peak at 2.3 +/- 0.1 eV.

The chemisorption of dibenzo[a,j]coronene on Si(001)-2 x 1.

Adsorption structures of the dibenzo[a,j]coronene (C(32)H(16)) molecule on the clean Si(001)-2 X 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with electronic structure calculations. The dibenzo[a,j]coronene molecules were found to adsorb on three different sites: one major adsorption site and two minor adsorption sites. The formation of four to eight Si-C covalent bonds is responsible for the different surface bonding structures observed. Bond strain effects due to out-of-plane bending of the molecule play a significant role in governing the surface bond energies. The geometries of the three adsorption sites were established by comparison of the experimental and simulated STM images. By applying an electrical pulse, the molecule can be made to hop from one site to another site without breaking the dibenzo[a,j]coronene molecular structure.

Localized deposition of coronene molecules on Si(001)-2x1 using a scanning tunneling microscope tip source.

The deposition of coronene molecules from scanning tunneling microscope (STM) tips onto a clean Si(001)-2x1 surface at 25 degrees C was investigated. The STM tips, contaminated with coronene, were found to deposit coronene molecules on the clean Si(001) surface, allowing patterns to be generated. Covalent Si-C chemical bonds, formed between the coronene molecules and the Si substrate, froze the flip-flop motion of the adjacent Si-Si dimers on the substrate. In most cases, the mode of coronene bonding to Si(001) is independent of whether deposition occurs from the gas phase or from the STM tip. Despite the covalent chemical bonds formed between the coronene molecule and the Si substrate, the STM tip can drag the coronene laterally on the Si substrate without inducing a chemical change in the molecule. Sharp spikes observed in the tunneling current during the coronene deposition reflect the abrupt decrease of the tip-substrate distance at the instant of transport of the molecule from tip to surface.

Local spectroscopy of image-potential-derived states: from single molecules to monolayers of benzene on Cu(111).

Stark-shifted image-potential states were measured with an STM tip for benzene adsorbed on a Cu(111) surface. A single benzene molecule locally shifts the position of the first image state toward the Fermi level by 0.2 eV relative to its position on the clean surface. The energetic position of this molecule-modified state shifts to lower energy with increasing coverage of benzene on the surface. This is attributed to local surface potential changes that are correlated with the lowering of the crystal work function due to adsorption of benzene.

Light-induced charge separation in anatase TiO2 particles.

Ultraviolet light-induced electron-hole pair excitations in anatase TiO(2) powders were studied by a combination of electron paramagnetic resonance and infrared spectroscopy measurements. During continuous UV irradiation in the mW.cm(-2) range, photogenerated electrons are either trapped at localized sites, giving paramagnetic Ti(3+) centers, or remain in the conduction band as EPR silent species which may be observed by their IR absorption. Using low temperatures (90 K) to reduce the rate of the electron-hole recombination processes, trapped electrons and conduction band electrons exhibit lifetimes of hours. The EPR-detected holes produced by photoexcitation are O(-) species, produced from lattice O(2-) ions. It is found that under high vacuum conditions, the major fraction of photoexcited electrons remains in the conduction band. At 298 K, all stable hole and electron states are lost from TiO(2). Defect sites produced by oxygen removal during annealing of anatase TiO(2) are found to produce a Ti(3+) EPR spectrum identical to that of trapped electrons, which originate from photoexcitation of oxidized TiO(2). Efficient electron scavenging by adsorbed O(2) at 140 K is found to produce two long-lived O(2)(-) surface species associated with different cation surface sites. Reduced TiO(2), produced by annealing in vacuum, has been shown to be less efficient in hole trapping than oxidized TiO(2).

Photooxidation of a mustard gas simulant over TiO2-SiO2 mixed-oxide photocatalyst: site poisoning by oxidation products and reactivation.

The photooxidation of 2-chloroethyl ethyl sulfide (2-CEES), a simulant for mustard gas, was studied using transmission IR spectroscopy on a mixed-oxide TiO2-SiO2 photocatalyst. Ultraviolet irradiation in the photon energy range from 2.1 to 5 eV was employed at a catalyst temperature of 200 K. Rapid photooxidation was observed by the loss of infrared intensity in the v(CHx) stretching region, and concomitant infrared features of adsorbed oxidation products were observed to develop. The oxidation products, captured on the photocatalyst at 200 K, were found to block 2-CEES readsorption. Upon heating the poisoned photocatalyst to about 300 K, infrared measurements indicate that the adsorbed CO2 oxidation product was desorbed. The capability for full readsorption of 2-CEES was achieved upon heating the poisoned photocatalyst to 397 K, and continued rapid photooxidation of the 2-CEES was then possible at about 1/3 the rate found for the fresh catalyst. Thus thermal treatment at 397 K of oxidation-product-poisoned TiO2-SiO2 material is able to partially restore the TiO2-SiO2 photooxidation activity.

Color vision with rapid-onset acceleration.

INTRODUCTION: Only sporadic information exists concerning perceived color shifts at increased G-loads. The purpose of this study was to investigate whether or not color vision is affected by rapid onset high G7-loads up to +9 Gz, and specifically whether perception of hue changes. METHODS: There were 10 male subjects, 9 with normal color vision and 1 with red-green protanomaly, all accustomed to Gz-loads in a human centrifuge. Each subject was tested on a total of 60 Gz-exposures with 10 s periods at +3, +5, +7, and +9 Gz in the centrifuge on three different days. G-onset rate was 6 G x s(-1). The subjects wore an anti-G suit and performed straining maneuvers if necessary to maintain vision. Five square color stimuli of medium saturation (yellow, red, blue, green, and gray) were projected one at a time on a screen in front of the subject, who gave his hue response orally. RESULTS: In 96.6% of exposures to various Gz-loads, the subjects responded by correctly naming colors. (The statistical analyses of the results were done for the subjects with normal color vision, with the protanomalous subject excluded.) Hue shifts occurred at the higher +Gz-levels, including 7.7% of the +9 Gz exposures. Yellow was the hue most frequently perceived as changed. Hue shifts were reported for yellow in 11% and 16% of the +7 and +9 Gz exposures, respectively. Hue shifts at +9 Gz occurred as frequently as blackout and G-LOC together. However, statistical analyses showed no significant effects for +Gz-load. CONCLUSIONS: Absolute identification of the color stimuli of medium saturation was stable and was not significantly affected by the rapid onset +Gz-loads up to and including +9 Gz.

Adsorption geometry of 4-picoline chemisorbed on the Cu(110) surface: a study of forces controlling molecular self-assembly.

The adsorption of 4-picoline (4-methylpyridine) on the Cu(110) surface has been studied with time-of-flight electron stimulated desorption ion angular distribution (TOF-ESDIAD) and other methods. Using deuterium labeling in the methyl group and hydrogen labeling on the aromatic ring, it has been possible to separately monitor by TOF-ESDIAD the C-D bond directions and the C-H bond directions in the adsorbed molecule. These triangulation measurements have led to a detailed understanding of the conformation of the adsorbed molecule relative to the Cu(110) crystal lattice, allowing one to witness changes in the molecular conformation as adsorbate-adsorbate interactional effects take place for increasing coverages. At low coverages, the molecule adsorbs by the N atom at an atop Cu site with the aromatic ring parallel to the <001> azimuth and with the molecular axis inclined 33 (+/- 5) degrees along the <001> azimuth. As rows of 4-picoline molecules form long range ordered chain structures oriented along the <112> azimuth, the aromatic ring twists 29 degrees about the inclined molecular axis as a result of forces between the adsorbate molecules. The initial tilting of the molecular axis at low coverage is likely due to the interaction of the positive-outward dipole with its image in the substrate. The ring twist may result from dipoleminus signdipole forces between the adsorbate molecules in the rows formed tending to form nested parallel pyridine rings. These studies are the first to apply the TOF-ESDIAD method for the measurement of the direction of chemical bonds at more than one molecular location within an adsorbed molecule and the new method is named electron stimulated desorption-molecular triangulation (ESD-MT). The results obtained give information of importance in understanding the factors which control conformational effects during the molecular self-assembly of complex adsorbed molecules on surfaces.

Electrostatic field enhancement of Al(111) oxidation.

We show that the electrostatic charging of an aluminum oxide film by electron-bombardment produces a greatly enhanced rate of Al(111) oxidation by O2(g) at 90 K, compared to a film which has not been bombarded by electrons. This novel memory effect for prior electron irradiation is caused by the negative electrostatic potential created and stored on the outer oxide film surface as a result of electron bombardment. The high electrostatic field ( approximately 10(7) V/cm) produced across the depth of the film is postulated to cause an enhancement of ion migration through the film, leading to rapid oxide film growth, as predicted by the Cabrera-Mott theory of low temperature metal oxidation.

Oxygen-containing functional groups on single-wall carbon nanotubes: NEXAFS and vibrational spectroscopic studies.

Single-walled nanotubes (SWNTs) produced by plasma laser vaporization (PLV) and containing oxidized surface functional groups have been studied for the first time with NEXAFS. Comparisons are made to SWNTs made by catalytic synthesis over Fe particles in high-pressure CO, called HiPco material. The results indicate that the acid purification and cutting of single-walled nanotubes with either HNO3/H2SO4 or H2O2/H2SO4 mixtures produces the oxidized groups (O/C = 5.5-6.7%), which exhibit both pi*(CO) and sigma*(CO) C K-edge NEXAFS resonances. This indicates that both carbonyl (C=O) and ether C-O-C functionalities are present. Upon heating in a vacuum to 500-600 K, the pi*(CO) resonances are observed to decrease in intensity; on heating to 1073 K, the sigma*(CO) resonances disappear as the C-O-C functional groups are decomposed. Raman spectral measurements indicate that the basic tubular structure of the SWNTs is not perturbed by heating to 1073 K, based on the invariance of the ring breathing modes upon heating. The NEXAFS studies agree well with infrared studies which show that carboxylic acid groups are thermally destroyed first, followed by the more difficult destruction of ether and quinone groups. Single-walled nanotubes produced by the HiPco process, and not treated with oxidizing acids, exhibit an O/C ratio of 1.9% and do not exhibit either pi*(CO) or sigma*(CO) resonances at the detection limit of NEXAFS. It is shown that heating (to 1073 K) of the PLV-SWNTs containing the functional groups produces C K-edge NEXAFS spectra very similar to those seen for the HiPco material. The NEXAFS spectra are calibrated against spectra measured for a number of fused-ring aromatic hydrocarbon molecules containing various types of oxidized functional groups present on the oxidized SWNTs.

Protection to +12 Gz.

BACKGROUND: The U.S. Air Force has developed +Gz-protective equipment that will provide most pilots protection to +9 Gz with minimal-to-no straining. This equipment includes a pressure breathing system called COMBAT EDGE (CE), which is currently operational, and the Advanced Technology Anti-G Suit (ATAGS), which is not yet operational. For future high-performance aircraft design it is important to know the upper limit of various protective equipment and techniques. METHODS: Six subjects were randomly exposed to a 12-cell matrix composed of +Gz and the following combinations of protective equipment at three seat-back angles (13 degrees, 30 degrees and 55 degrees from the vertical): 1) the standard CSU-13B/P anti-G suit (STD); 2) the STD suit with CE; 3) the ATAGS; and 4) the ATAGS with CE. Relaxed, followed by straining +Gz tolerance was determined using 15-s rapid onset runs to a maximum of +12 Gz. A comprehensive battery of baseline and post-exposure medical surveillance studies was performed to evaluate the medical consequences of these high +Gz exposures. RESULTS: All 6 subjects were able to achieve +12 Gz with various combinations of +Gz-protective equipment, seat-back angle, and various amounts of straining, from none to maximum. When the data were collapsed over all protective equipment there was a significant (p < 0.05) seat effect. Relaxed tolerance to ROR increased with seat-back angle from 13 degrees to 30 degrees to 55 degrees. There was also a significant protective equipment effect when the data were collapsed over all seat-back angles. CONCLUSIONS: These data confirm that effortless protection to +9 Gz is available using ATAGS/CE with the 13 degree and 30 degree seat-back angle (F-15, F-16 and F-22) and to +10.5 Gz with a 55 degree seat-back angle. Moreover, with ATAGS/CE, and a moderate degree of straining, +12 Gz is definitely achievable at 55 degrees, even with reduced anti-G suit pressure at 55 degrees. With additional straining +12 GC is also achievable at the 13 degree and 30 degree seat-back angles.

Color vision deficits and laser eyewear protection for soft tissue laser applications.

PURPOSE: Laser safety considerations require urologists to wear laser eye protection. Laser eye protection devices block transmittance of specific light wavelengths and may distort color perception. We tested whether urologists risk color confusion when wearing laser eye protection devices for laser soft tissue applications. MATERIALS AND METHODS: Subjects were tested with the Farnsworth-Munsell 100-Hue Test without (controls) and with laser eye protection devices for carbon dioxide, potassium titanyl phosphate (KTP), neodymium (Nd):YAG and holmium:YAG lasers. Color deficits were characterized by error scores, polar graphs, confusion angles, confusion index, scatter index and color axes. Laser eye protection device spectral transmittance was tested with spectrophotometry. RESULTS: Mean total error scores plus or minus standard deviation were 13+/-5 for controls, and 44+/-31 for carbon dioxide, 273+/-26 for KTP, 22+/-6 for Nd:YAG and 14+/-8 for holmium:YAG devices (p <0.001). The KTP laser eye protection polar graphs, and confusion and scatter indexes revealed moderate blue-yellow and red-green color confusion. Color axes indicated no significant deficits for controls, or carbon dioxide, Nd:YAG or holmium:YAG laser eye protection in any subject compared to blue-yellow color vision deficits in 8 of 8 tested with KTP laser eye protection (p <0.001). Spectrophotometry demonstrated that light was blocked with laser eye protection devices for carbon dioxide less than 380, holmium:YAG greater than 850, Nd:YAG less than 350 and greater than 950, and KTP less than 550 and greater than 750 nm. CONCLUSIONS: The laser eye protection device for KTP causes significant blue-yellow and red-green color confusion. Laser eye protection devices for carbon dioxide, holmium:YAG and Nd:YAG cause no significant color confusion compared to controls. The differences are explained by laser eye protection spectrophotometry characteristics and visual physiology.

Color vision deficits during laser lithotripsy using safety goggles for coumarin green or alexandrite but not with holmium:YAG laser safety goggles.

PURPOSE: Laser lithotripsy requires urologists to wear laser eye protection. Laser eye protection devices screen out specific light wavelengths and may distort color perception. This study tests whether urologists risk color confusion when wearing laser eye protection devices for laser lithotripsy. MATERIALS AND METHODS: Urologists were tested with the Farnsworth Dichotomous Test for Color Blindness (D-15) and the Farnsworth-Munsell 100-Hue Test (FM-100) without (control) and with laser eye protection devices for coumarin green, alexandrite and holmium:YAG lasers. Error scores were tabulated. The pattern of color deficits was characterized with confusion angles, confusion index (C-index), scatter index (S-index) and color axes. Laser eye protection devices were tested with spectrophotometry for spectral transmittance and optical density. RESULTS: The D-15 transposition errors (mean plus or minus standard deviation) for control, holmium:YAG, alexandrite and coumarin green laser eye protection were 0 +/- 0, 0 +/- 0, 0.3 +/- 0.5 and 6.4 +/- 1.6, respectively (p = 0.0000001). The FM-100 error scores (mean plus or minus standard deviation) were 20 +/- 15, 20 +/- 14, 91 +/- 32 and 319 +/- 69, respectively (p = 0.0001). The confusion index scores indicated a mild color confusion for the alexandrite and pronounced color confusion for the coumarin green laser eye protection. The confusion angles and scatter indexes mimicked a congenital blue-yellow deficit for coumarin green laser eye protection. Color axes showed no significant deficits for control or holmium:YAG laser eye protection in any subject, red-green axis deficits in 3 of 6 tested with alexandrite and blue-yellow axis deficits in 12 of 12 tested with coumarin green (p < 0.001). Spectrophotometry showed that laser eye protection for coumarin green blocks light less than 550 nm., alexandrite blocks light greater than 650 nm. and holmium:YAG blocks light greater than 825 nm. CONCLUSIONS: Laser eye protection for coumarin green causes pronounced blue-yellow color confusion, whereas alexandrite causes mild red-green color confusion among urologists, holmium:YAG causes no significant color confusion compared to controls. The differences are explained by laser eye protection spectrophotometry characteristics and visual physiology.

Tracking the motion of chemisorbed molecules on their adsorption sites.

A new method, the time of flight-electron-stimulated desorption ion angular distribution method (TOF-ESDIAD), is described. The method permits the mapping of the lateral momentum distribution of adsorbed species on their adsorption sites. Examples of the study of the rotation of chemisorbed PF3 molecules and the frustrated lateral translation of chemisorbed CO molecules, both on single-crystal metal surfaces, are given. The observed anisotropy of the frustrated translation of CO is postulated to occur as a result of the 2pi* orbital alignment in chemisorbed CO along the close packed direction of the Cu(110) substrate.

Parallel pathways, noise masking and glaucoma detection: behavioral and electrophysiological measures.

PURPOSE: We tested the hypothesis that because of their reduced neural efficiency, glaucoma patients should have increasingly impaired thresholds as external noise is added to a stimulus. METHOD: We compared the performance of 20 normals (mean age = 39 years) with that of 15 patients with early glaucoma or at very high risk for glaucoma (mean age 45 years). All patients had normal visual acuity. Contrast thresholds were measured on two sets of tasks: (1) behavioral and (2) sweep visually evoked potentials (VEPs). Two stimuli were used (a) 7.5 Hz reversing gratings of 0.69 cpd, and (b) 5.5 cpd gratings. Noise was binary and contrast varied from 0 to 80%. Psychophysical thresholds were determined using a staircase which employed a spatial four alternative forced choice procedure (4AFC) and converged on 50% correct. Sweep VEP thresholds were determined by extrapolation to zero volts as a function of log contrast. RESULTS: Differences between normal subjects and patients with early glaucoma were not significant without noise. Both the absolute size of the difference and its significance increased as noise level increased. For the behavioral thresholds these trends were clearer with the 5.5 cpd grating, while for the sweep VEPs they were more clear for the 0.69 cpd grating. CONCLUSION: The performance deficit of glaucoma patients which may be minimal under normal testing conditions is magnified when external noise is added to the stimulus. VEPs and psychophysical thresholds show interesting differences in their sensitivity to this effect. Implications for the early detection of glaucoma are discussed.

Contrast sensitivity and disability glare in the middle years.

Spatial contrast sensitivity and disability glare were measured in a large sample (n = 90, 30 per decade) of middle-aged subjects, aged 21-50 years, who had clear media and were ophthalmologically normal. We found no significant differences in the contrast sensitivities as a function of age in the middle years for (1) gratings generated on a monitor; (2) interference gratings generated in the retinal plane; (3) gratings in the presence of glare; and (4) mesopic increment thresholds with and without glare. The large sample size provides sufficient statistical power (0.8) for one to conclude that contrast sensitivity, optical quality, and foveal neural sensitivity are unlikely to vary more than 0.1 log unit between the ages of 21 and 50 in ophthalmologically normal subjects with clear media.

Direct observation of chemical bond dynamics on surfaces.

The dynamics of chemisorbed species as they swing to-and-fro on their adsorption sites may be directly observed with electron-stimulated desorption. The observation of the thermal disorder in adsorbate chemical bond directions, through studies of the thermal excitation of librational modes, allows one to visualize the potential energy surfaces controlling the structure and dynamics of adsorbates on single crystal metal and semiconductor surfaces. This information may be useful in understanding surface diffusion as well as the spatial aspects of surface chemical reactions.

Contrast sensitivity: characteristics of a large, young, adult population.

Contrast sensitivity functions and complete eye examinations were obtained from 103 normal, healthy young adults (ages 21 to 40 years). Descriptive statistics were compiled for the group in order to provide normative information. Subsets of the population were evaluated with respect to the relations among the attributes of accommodation, visual acuity, refraction, spectacle wear, and contrast sensitivity. The influence of age in this restricted population was seen only at 16 cpd. In those subjects with better than 6/6 (20/20) Snellen acuity, there were statistically significant relations with the parameters of the contrast sensitivity function as compared to those observers with 6/6 (20/20) or poorer acuity. High spatial frequency resolution was significantly better for those observers with better than 6/6 (20/20) acuity in either eye. In addition, this study provides a broad base of normative data for variability from a large population confined to a specific age range and with refractive errors that ranged from minimal to more than average.