Electronic transitions of Ar,Xe, N2, CO physisorbed on Ag(111) and Al(111)

High Resolution Electron Energy Loss Spectroscopy has been extended to study also the excitonic (low lying electronic) transitions of physisorbed rare gas atoms (Ar, Xe) and diatomic molecules (N₂, CO) on Ag(111) and Al(111) surfaces at ～20K. Electron Loss Spectra were performed using a pair of hemispherical analyzers mounted at a fixed scattering angle (90°). This spectrometer allowed high transmission in the range of 0–15eV loss energies and incident beam energies up to 2OeV. AES, LEED and UV Photoemission (HeI) were also used in situ to characterize these surfaces and to identify the adsorbed gases and delineate their absolute coverage regimes.In contrast to optical absorption experiments, we observe both, optical (dipole) forbidden and allowed electronic transitions which show vibrational line structure for condensed multilayers. By comparison to gas phase data we find only weak perturbations in the condensed state. The observed electronic excitations show changes in intensity and FWHM depending on the coverage of the adsorbed gases.The FWHM of the electronic excitations of CO and N₂ adsorbed in the monolayer regime is larger than in multilayers. Nitrogen, on both surfaces exhibits an increase from 60meV to 120meV (FWHM) whereas for CO the vibronic features are broadened out leaving peaks with FWHM of ～1eV.The intensities of the electronic losses for all gases are smaller in the first monolayer than in the second or in multilayers. At submonolayer coverage the loss intensifies due to electronic excitations are strongly reduced and no longer observable although vibrational bands and photoelectron spectra show the presence of physisorbed adsorbates.Our results will be compared to optical absorption experiments (ref.1) on similar systems and to atom-on-jellium calculations (ref.2).     

Invariance of the essential spectra for perturbations with unbounded hard cores

Based on the Feynman-Kac formula and a certain variant of Weyl's theorem, we determine the essential spectra of Schrödinger operators including unbounded hard cores.     

Nonspecific laryngeal granuloma: A case study of a professional singer

A professional singer with laryngeal granuloma underwent surgery following failed response to conservative treatments. Two primary findings emerged. First, although a sizable lesion was present initially, presurgical voice measures were largely normal or superior. The exception was elevated phonatory effort during singing. Second, postsurgical voice functions were entirely normal or superior (including phonatory effort), despite demanding singing performances a few weeks following surgery. The results add to the limited corpus of quantitative, normative-referenced data on voice in patients with granulomas and are inconsistent with previous reports of voice abnormalities in such patients and poor functional response to surgery.     

Methotrexate analogs. 7. Synthesis of two higher homologs and a positional isomer of methotrexate diethyl ester as potential antitumor agents

Analogs of methotrexate diethyl ester ( 1 ) were prepared, in which the distances separating the ester functions from each other and from the carboxamide function of the p-aminobenzoate moiety were varied via the use of methylene groups as “spacers”. The diethyl esters 3 and 4 , with D,L-α-aminoadipate and D,L-α-aminopimelate side chains in place of L-glutamate, displayed approximately the same order of activity as compound 1 against bacterial and mammalian cells in culture, and were inhibitors of the enzyme dihydrofolate reductase. When given intraperitoneally to L1210 1eukemic mice at a dose of 120 mg./kg. q3d 1,4,7, compound 4 produced a 67% increase in survival and no evidence of toxicity, whereas methotrexate diethyl ester ( 1 ) gave a 44% increase in survival at a dose of 45 mg./kg. q3d 1,4,7 but was toxic at higher doses. The positional isomer 2 was inactive.     

Surface and aggregation behavior of aqueous solutions of Ru(II) metallosurfactants. 3. Effect of chain number and orientation on the structure of adsorbed films of [Ru(bipy)2(bipy')]Cl2 complexes

The surface behavior of a range of surfactant [Ru(bipy)(2)(p,p'-dialkyl-2,2'-bipy)]Cl(2) complexes, which we express as Ru(q)(p)C(n) where n is the alkyl chain length, p refers to the substitution position on the bipyridine ligand (=4 or 5), and q (=1 or 2) is the number of substituted alkyl chains, has been examined using neutron reflectometry. The adsorption of the single-chain Ru(1)(4)C(19) and Ru(1)(5)C(19) surfactants is strongly time-dependent, taking in excess of 10 h to form an equilibrium film. It is suggested that the slow adsorption rate is related to the alkyl chain length rather than the low monomer concentration present in the solutions. At concentrations below the critical micelle concentration (cmc) of Ru(1)(4)C(19), the film of Ru(1)(5)C(19) is denser than that of Ru(1)(4)C(19) at comparable concentration, consistent with the mass densities of the bulk solids, whereas at concentrations close to and greater than this cmc the converse pertains. Close to the cmc, the adsorbed films possess an average area per molecule significantly less than the nominal headgroup area of the surfactants (approximately 30 angstroms(2) compared with approximately 100 angstroms(2)). This fact together with consideration of the thickness and density of the adsorbed films leads to the conjecture that surface aggregates may be the adsorbing units. The adsorption of the double-chain surfactant Ru(1)(p)C(19), in contrast to the behavior of the Ru(1)(p)C(19) surfactants, is weak and independent of time. This behavior is attributed to the alkyl chain orientation. The adsorption behavior of a racemic mixture of the Delta and Lambda isomers of Ru(2)(4)C(19) has been compared with that of the Delta isomer. It is found that the film of racemic material is more closely packed than that of the resolved complex.     

Resolvable and near-resolvable decompositions ofDK v into oriented 4-cycles

Summary A resolvableX-decomposition ofDK _v (the complete symmetric digraph onv vertices) is a partition of the arcs ofDK _v into isomorphic factors where each factor is a vertex-disjoint union of copies ofX and spans all vertices ofDK _v . There are four orientations ofC ₄ (the 4-cycle), only one of which has been considered: Bennett and Zhang, Aequationes Math.40 (1990), 248–260. We give necessary and sufficient conditions onv for resolvableX-decomposition ofDK _v , whereX is any one of the other three orientations ofC ₄. A near-resolvableX-decomposition ofDK _v is as above except that each factor spans all but one vertex ofDK _v . Again, one orientation ofC ₄ has been dealt with by Bennett and Zhang, and we provide necessary and sufficient conditions onv for the remaining three cases. The construction techniques used are both direct (for small values ofv) and recursive.The author thanks Simon Fraser University for its support during her graduate studies when the research for this paper was undertaken.The author acknowledges the Natural Sciences and Engineering Research Council of Canada for financial support under grant A-7829.     

Acoustic response from adherent targeted contrast agents

In ultrasonic molecular imaging, encapsulated micron-sized gas bubbles are tethered to a blood vessel wall by targeting ligands. A challenging problem is to detect the echoes from adherent microbubbles and distinguish them from echoes from nonadherent agents and tissue. Echoes from adherent contrast agents are observed to include a high amplitude at the fundamental frequency, and significantly different spectral shape compared with free agents (p <0.0003). Mechanisms for the observed acoustical difference and potential techniques to utilize these differences for molecular imaging are proposed.     

Intermolecular vibrational coherence in bacteriochlorophyll a with clustered polar solvent molecules

We show that resonant impulsive excitation of the Qy absorption band of bacteriochlorophyll a (BChl) launches a rapidly damped (gamma < 200 fs) ground-state coherent wave-packet motion that arises from intermolecular modes with clustered solvent molecules. Femtosecond pump-probe, dynamic-absorption signals were obtained at room temperature with BChl solutions in pyridine, acetone, and 1-propanol. The vibrational coherence observed in the 0-800-fs regime is modeled in the time domain by two (or three, in the case of 1-propanol) modulation components with asymmetric, inhomogeneously broadened line shapes and frequencies in the 100-200-cm(-1) range. The mean frequency of the vibrational coherence exhibits at least a quadratic dependence on the dipole moment of the solvent molecules and a y-intercept in the 100-cm(-1) regime. This trend is modeled by an expression for the natural frequency of a "6-12" potential composed of attractive terms from van der Waals forces and a repulsive term from the exchange (Pauli exclusion) force. The model suggests that comparable contributions to the potential are provided by the dipole-dipole and London dispersion interactions. These results support the hypothesis that the low-frequency vibrational modes in the 100-cm(-1) regime that are coupled to the light-driven charge-separation reactions in the reaction center from purple bacteria are derived from intermolecular vibrational modes between the chromophores and the surrounding protein medium.