Hamiltonian theory for vibrational line shapes of atoms adsorbed on surfaces

The vibrational motions of atomic adsorbates on surfaces can be probed by helium atom scattering. The experimental observable is the dynamic structure factor, which shows an inelastic peak around the vibrational frequency of the isolated adsorbates known as the frustrated translational or T-mode peak. In this paper we develop a theory for the line shape of this peak, as well as for its temperature-dependent shift and broadening, based on a Hamiltonian equivalent of the generalized Langevin equation. The theory can be used to infer physical parameters of the adatom-surface interaction, such as the friction coefficient, the barrier height to diffusion, and the anharmonicity parameter. Numerical simulations are used to ascertain the range of validity of the theory, which is also generalized to describe multidimensional systems and to include quantum corrections. We compare the theoretical predictions for the shift and broadening with experimental results for the Na/Cu(001) system, showing quantitative agreement within experimental resolution.     

Studies on quinones. VII. Synthesis of some benzo[b]thiophene-4,7-diones

The synthesis of methyl 4,7-dihydro-4,7-dioxobenzo[b]thiophene-2-carboxylate ( 20 ) based on the reaction of methyl mercaptoacetate with activated 1,4-benzoquinones is described. Methyl 4,7-dihydro-4,7-dioxo-5-hydroxybenzo[b]thiophene-2-carboxylate ( 24 ) and its corresponding methyl ether 26 were obtained through a Thiele-Winter acetoxylation on 20 . On the basis of the properties of methyl 4,7-dihydro-4,7-dioxo-6-methoxy-benzo[b]thiophene-2-carboxylate ( 21 ) obtained from 2,4,5-trimethoxybenzaldehyde ( 32 ), the structures of the products 24 and 26 are proposed.     

Relation between the melting temperature and the temperature of maximum density for the most common models of water

Water exhibits a maximum in density at normal pressure at 4 degrees above its melting point. The reproduction of this maximum is a stringent test for potential models used commonly in simulations of water. The relation between the melting temperature and the temperature of maximum density for these potential models is unknown mainly due to our ignorance about the melting temperature of these models. Recently we have determined the melting temperature of ice I(h) for several commonly used models of water (SPC, SPC/E, TIP3P, TIP4P, TIP4P/Ew, and TIP5P). In this work we locate the temperature of maximum density for these models. In this way the relative location of the temperature of maximum density with respect to the melting temperature is established. For SPC, SPC/E, TIP3P, TIP4P, and TIP4P/Ew the maximum in density occurs at about 21-37 K above the melting temperature. In all these models the negative charge is located either on the oxygen itself or on a point along the H-O-H bisector. For the TIP5P and TIP5P-E models the maximum in density occurs at about 11 K above the melting temperature. The location of the negative charge appears as a geometrical crucial factor to the relative position of the temperature of maximum density with respect to the melting temperature.     

Thermodynamic properties and aggregate formation of surfactant-like molecules from theory and simulation

The goal of this work is twofold: to predict the phase equilibria behavior of simplified surfactant models and to predict the population of aggregates as a function of pressure. We compare Monte Carlo simulation results of these systems with predictions from a modified version of the statistical associating fluid theory (soft-SAFT). Surfactant-like molecules are modeled as Lennard-Jones chains of tangent segments with one or two association sites. We study the influence of the number and location of the association sites on the thermodynamic properties and fraction of nonbonded molecules in all cases. The influence of the chain length is also investigated for a particular location of the sites. Results are compared with NPT Monte Carlo simulations to test the accuracy of the theory, and to study the molecular configurations of the system. Soft-SAFT is able to quantitatively predict the MC PVT results, independently of the location of the association sites. The theory is also able to capture the qualitative trend of the population of aggregates with pressure. Quantitative agreement is only obtained for specific locations of the sites.     

Zinc(II) complexes with intramolecular amide oxygen coordination as models of metalloamidases

Polydentate ligands (6-R1-2-pyridylmethyl)-R2(R1= NHCOtBu, R2= bis(2-pyridylmethyl)amine L1, bis(2-(methylthio)ethyl)amine L2 and N(CH2CH2)2S L3) form mononuclear zinc(II) complexes with intramolecular amide oxygen coordination and a range of coordination environments. Thus, the reaction of Zn(ClO4)2.6H2O with L1-3 in acetonitrile affords [(L)Zn](ClO4)2(L=L1, 1; L2, 2) and [(L3)Zn(H2O)(NCCH3)](ClO4)2 3. The simultaneous amide/water binding in resembles the motif that has been proposed to be involved in the double substrate/nucleophile Lewis acidic activation and positioning mechanism of amide bond hydrolysis in metallopeptidases. X-ray diffraction, 1H and 13C NMR and IR data suggests that the strength of amide oxygen coordination follows the trend 1>2 >3. L1-3 and undergo cleavage of the tert-butylamide upon addition of Me4NOH.5H2O (1 equiv.) in methanol at 50(1)degrees C. The rate of amide cleavage follows the order 1> 2> 3, L1-3. The extent by which the amide cleavage reaction is accelerated in 1-3 relative to the free ligands, L1-3, is correlated with the strength of amide oxygen binding and Lewis acidity of the zinc(II) centre in deduced from the X-ray, NMR and IR studies.     

Daily doses of biologically active UV radiation retrieved from commonly available parameters

A multiple linear correlation is done between atmospheric transmissivity for four biologically active radiation daily doses (UVB, erythemal, DNA and plant damage) T, and three parameters (daily sunshine fraction σ, cosine of the daily minimum solar zenith angle μ_min and daily total ozone column Ω). T is defined as the ratio of a daily dose to its extra‐atmospheric value. The data used are spectral UV measurements (390–400 nm at 0.5 nm step) recorded along year 2000 and over 8 months of year 2001 at Briançon Station (Alps, 1300 m above sea level) that forms part of the French UV network. The coefficients obtained from year 2000 correlation permit to retrieve daily doses for year 2001 with an average error running from 3 to 9% for monthly mean values and from 2 to 4.5% for 3‐monthly mean values, depending on daily dose type. The retrieval of yearly mean value gives an error between 4 and 7.5%. Retrieving the daily dose of a given day, where σ≥ 0.2, introduces error running from 16 to 32% depending on daily dose. An attempt to retrieve the yearly mean UVB daily dose for a northern France site, from the previous coefficients, gives encouraging results.     

Isomer yield ratios and cross sections for110(4.9 h)In/110(69 min)In and108(58 min) In/108(39.6 min)In produced by alpha reactions on silver

This paper reports the determination of absolute excitation functions and cross section ratios for the production of 110(4.9 h)/110(69 min) In and^{108(58 min)/108(39.6 min)}In in reactions of -particles with natural silver. Target stack foils of silver were bombarded with the 55.0 MeV -particle, beam available at the Buenos Aires synchrocyclotron. The -spectrometry was used for the identification and for the determination of the absolute activity of^{110(4.9 h)}In and^{110(69 min)}In from¹⁰⁷Ag/, n/ and¹⁰⁹Ag/, 3n/ reactions and of^{108(58 min)}In and^{108(39.6 min)}In from¹⁰⁷Ag/, 3n/ and¹⁰⁹Ag/, 5n/ reactions by means of Ge intrinsic detector.This work has been sponsored by the Subsecretaria de Ciencia y Tecnología Argentina.     

Oxidative stress and defence mechanisms of the freshwater cladoceran Daphnia longispina exposed to UV radiation

The aim of the present study is to evaluate the occurrence of oxidative stress in the cladoceran Daphnia longispina exposed to UV-A and UV-B radiation. The activity of antioxidant enzymes and lipid peroxidation markers is investigated and the protective action of ascorbic acid determined. Results show differences in the lethality radioinduced by UV-A and UV-B. Both UV-A and UV-B exposure cause an important increase in malonaldehyde (MDA) concentration and catalase activity. Ascorbic acid addition reduces the MDA concentration, indicating that the oxidative stress caused by either UV-A or UV-B radiation can be controlled by antioxidants. The increase of the antioxidant enzymes may be a response mechanism to oxidative stress.     

Density functional theory predictions of isotropic hyperfine coupling constants

The reliability of density functional theory (DFT) in the determination of the isotropic hyperfine coupling constants (hfccs) of the ground electronic states of organic and inorganic radicals is examined. Predictions using several DFT methods and 6-31G, TZVP, EPR-III and cc-pVQZ basis sets are made and compared to experimental values. The set of 75 radicals here studied was selected using a wide range of criteria. The systems studied are neutral, cationic, anionic; doublet, triplet, quartet; localized, and conjugated radicals, containing 1H, 9Be, 11B, 13C, 14N, 17O, 19F, 23Na, 25Mg, 27Al, 29Si, 31P, 33S, and 35Cl nuclei. The considered radicals provide 241 theoretical hfcc values, which are compared with 174 available experimental ones. The geometries of the studied systems are obtained by theoretical optimization using the same functional and basis set with which the hfccs were calculated. Regression analysis is used as a basic and appropriate methodology for this kind of comparative study. From this analysis, we conclude that DFT predictions of the hfccs are reliable for B3LYP/TZVP and B3LYP/EPR-III combinations. Both functional/basis set scheme are the more useful theoretical tools for predicting hfccs if compared to other much more expensive methods.