Photoemission study of oxygen chemisorption on tin

Photoemission measurements have been made at photon energies from 5–12 eV and at 21.2 eV on evaporated Sn films and the same films with varying room temperature exposure to oxygen. For hν ? 9 eV the quantum yield for Sn with exposures of as much as 4000 L oxygen (1 L = 1 Langmuir = 10^?6 Torr sec) differs only slightly from the clean metal. For hν ? 9 eV no change in yield is observed with oxygen exposure. The energy distribution of photoemitted electron (EDC's) from Sn with increasing exposure to oxygen above ? 20 L are characterized by the growth of two peaks which were not present in the EDC's for the clean metal, located 2.9 ± 0.1 eV and 4.8 ± 0.1 eV below the Fermi level. We associate this structure with the presence of SnO₂. No sharp resonance which could be associated with adsorbed oxygen was seen. Uniformly reduced emission from metallic Sn states and a Fermi level as sharp as for the clean metal is observed in the EDC's at all oxygen exposures. In addition, no change in work function with oxygen exposure was detected. The effects of oxygen saturate for exposures ? 4000 L. We suggest that under the conditions used in this experiment, the oxygen penetrates beneath the surface forming SnO₂ and leaving metallic Sn on the surface.     

Results of a joint auger/ESCA round robin sponsored by astm commitree E-42 on surface analysis: Part I. Esca results

We report results of a round robin involving binding-energy (BE) and relative-intensity measurements on high-purity samples of gold and copper by X-rayWe have conducted an extensive round robin involving ESCA or XPS measurements on high-purity samples of Ni, Au, and Cu. The Ni sample was used to estabThis round robin had three principal objectives. First, it was intended to assess the overall accuracy of BE and intensity measurements in XPS measuremSecond, it was intended to establish an empirical intensity calibration of one type of XPS instrument versus another from the reported intensity ratiosThird, it was desired to determine the peak position and peak shape for the carbon 1s photoelectron line originating for “adventitious” carbonaWe have made an extensive analysis of trends in the BE and intensity data. We have computed deviations of individual BE measurements from the median vaThe two types of plots just described based on BE and intensity data can be regarded as “response functions” that describe the performance of indivWe have invoked Occam's Razor to distinguish instruments with response functions which vary monotonically with electron energy from those instruments wThe reported spreads in BE and relative-intensity data reported here indicate that improved calibration and operating procedures are required for XPS m     

An example of cycling in a feasible point algorithm

An example shows that, if in Rosen's [4] algorithm for calculating a point that satisfies linear constraints a natural criterion is used to select constraints to delete from active sets, then the algorithm may cycle instead of converging. There are no degeneracies in the example.     

A note on quasi-newton formulae for sparse second derivative matrices

In order to apply quasi-Newton methods to solve unconstrained minimization calculations when the number of variables is very large, it is usually necessary to make use of any sparsity in the second derivative matrix of the objective function. Therefore, it is important to extend to the sparse case the updating formulae that occur in variable metric algorithms to revise the estimate of the second derivative matrix. Suitable extensions suggest themselves when the updating formulae are derived by variational methods [1, 3]. The purpose of the present paper is to give a new proof of a theorem of Dennis and Schnabel [1], that shows the effect of sparsity on updating formulae for second derivative estimates.     

Using monkeys to explore perceptual "loss" versus "learning" models in English and Spanish voice-onset-time perception

Cross-language research using synthetic voice-onset-time series over the past 40 years suggests that the Spanish lead contrast is acoustically less salient than the English lag contrast. This study examined monkey identification of a labial consonant-vowel voice-onset-time (CV VOT) series (-60 to +70 ms) in order to obtain a linguistically unbiased estimate of lead versus lag salience. Comparisons were made with both English and Spanish adult human listeners. In a classic two-choice identification test, monkey and Spanish functions were quite variable and showed evidence of sensitivity to three types of voicing cues (lead versus simultaneous versus lag). In contrast, English functions were highly categorical and showed sensitivity to only two types of cues (combined lead/simultaneous versus lag). Next, listeners were explicitly trained via feedback to differentiate stimuli crossing lead and lag boundaries. Here, monkey and Spanish performance was initially more symmetrical than English performance, with the latter showing reduced sensitivity to the lead boundary, but group differences disappeared after extended training. These results provide evidence for perceptual loss in English listeners for aspects of Spanish voicing lead perception.     

Fiber-optic infrared reflectance spectroelectrochemical studies of osmium and ruthenium nitrosyl porphyrins containing alkoxide and thiolate ligands

We have examined the redox behavior of the osmium and ruthenium compounds (OEP)M(NO)(OEt) and (OEP)M(NO)(SEt) (OEP = octaethylporphyrinato dianion; M = Os, Ru) by cyclic voltammetry and infrared spectroelectrochemistry. The compound (OEP)Os(NO)(OEt) undergoes a single reversible oxidation process in dichloromethane. In contrast, the thiolate compound (OEP)Os(NO)(SEt) undergoes a net irreversible oxidation resulting in formal loss of the SEt ligand. Extended Hückel calculations on crystal structures of these two compounds provide insight into the nature of their HOMOs. In the case of the alkoxide compound, the HOMO is largely metal centered, with 70% of the charge located in the metal's orbital and approximately 25% on the porphyrin ring. However, the HOMO of the thiolate compound consists of a pi bonding interaction between the metal dxz orbital and the px orbital on the sulfur, and a pi antibonding interaction between the metal d orbital and a pi* orbital on NO. The redox behavior of the Ru analogues have been determined, and are compared with those of the Os compounds.     

Dependence of the AES backscattering correction factor on the experimental configuration

We present an analysis of the dependence of the backscattering correction factor (BCF) in Auger-electron spectroscopy (AES) on the analyzer acceptance angle. Illustrative BCF calculations are presented for Pd M₅N₄₅N₄₅ Auger electrons as a function of primary-electron energy for primary-electron angles of incidence, θ₀, of 0° and 80° and for various values of the analyzer acceptance angle. It was necessary to generalize the BCF definition for the case of an analyzer with an arbitrarily large acceptance angle; this was done with a new function, the integral emission depth distribution function. BCFs calculated from an advanced model of electron transport in the surface region of the Pd sample varied weakly with analyzer half-cone angle for θ₀ = 0° but more strongly for θ₀ = 80° where there were BCF differences varying between 19% at a primary energy of 1 keV and 6% at a primary energy of 5 keV. These BCF differences are due in part to variations of the BCF with emission angle and in part to variations of the density of inner-shell ionizations within the information depth for the detected Auger electrons. The latter variations are responsible for differences larger than 10% between BCFs from the widely used simplified BCF model and those from the more accurate advanced model for primary energies less than about 5 keV for θ₀ = 80°. For normal incidence of the primary beam, differences greater than 10% between BCFs from the simplified and advanced models were found for primary energies between 1 keV and 4 keV. These BCF differences indicate that the simplified model can provide only approximate BCF values. In addition, the simplified model does not provide any BCF dependence on Auger-electron emission angle or analyzer acceptance angle.