Photodissociation of HCl and small (HCl)m complexes in and on large Ar n clusters

Photodissociation experiments were carried out at 193 nm for single HCl molecules which are adsorbed on the surface of large Ar n clusters and small (HCl)m complexes which are embedded in the interior of these clusters. For the surface case the size dependence is measured for the average sizes n=140-1000. No cage exit events are observed in agreement with the substitutional position of the molecule deeply buried in the outermost shell. This result is confirmed by a molecular dynamics simulation of the pickup process under realistic conditions concerning the experiment and the interaction potentials. The calculations of the dissociation process employ the surface hopping model. For the embedded case the average sizes covered are m=3 and 6 and n=8-248. The kinetic energy of the H atom fragments is measured exhibiting peaks at zero and around 2.0 eV which mark completely caged and unperturbed fragments, respectively. The ratio of theses peaks strongly depends on the cluster size and agrees well with theoretical predictions for one and two closed icosahedral shells, in which the nonadiabatic coupling of all states was accounted for.     

Predicted stability and structure of (HXeCCH)n (n=2 or 4) clusters and of crystalline HXeCCH

Ab initio calculations predict the existence of the dimer and tetramer of HXeCCH. The interaction energies are -6.66 and -19.40 kcal mol-1 for the dimer and tetramer, respectively. For both complexes, larger blue shifts of the Xe-H stretching mode are found, while the Xe-C stretching modes are slightly redshifted. The stability and structure of HXeCCH crystals is predicted by density functional theory calculations with periodic boundary conditions. Strong electrostatic interactions are found between the monomers in the crystal. The results are first evidence for the existence of crystalline materials made of a novel class of noble gas molecules.     

Vibrational spectroscopy of (SO4(2-)).(H2O)n clusters, n=1-5: harmonic and anharmonic calculations and experiment

The vibrational spectroscopy of (SO4(2-)).(H2O)n is studied by theoretical calculations for n=1-5, and the results are compared with experiments for n=3-5. The calculations use both ab initio MP2 and DFT/B3LYP potential energy surfaces. Both harmonic and anharmonic calculations are reported, the latter with the CC-VSCF method. The main findings are the following: (1) With one exception (H2O bending mode), the anharmonicity of the observed transitions, all in the experimental window of 540-1850 cm(-1), is negligible. The computed anharmonic coupling suggests that intramolecular vibrational redistribution does not play any role for the observed linewidths. (2) Comparison with experiment at the harmonic level of computed fundamental frequencies indicates that MP2 is significantly more accurate than DFT/B3LYP for these systems. (3) Strong anharmonic effects are, however, calculated for numerous transitions of these systems, which are outside the present observation window. These include fundamentals as well as combination modes. (4) Combination modes for the n=1 and n=2 clusters are computed. Several relatively strong combination transitions are predicted. These show strong anharmonic effects. (5) An interesting effect of the zero point energy (ZPE) on structure is found for (SO4(2-)).(H2O)(5): The global minimum of the potential energy corresponds to a C(s) structure, but with incorporation of ZPE the lowest energy structure is C2v, in accordance with experiment. (6) No stable structures were found for (OH-).(HSO4-).(H2O)n, for n相似文献   

A mean field model for a class of garbage collection algorithms in flash-based solid state drives

Garbage collection (GC) algorithms play a key role in reducing the write amplification in flash-based solid state drives, where the write amplification affects the lifespan and speed of the drive. This paper introduces a mean field model to assess the write amplification and the distribution of the number of valid pages per block for a class $\mathcal {C}$ of GC algorithms. Apart from the Random GC algorithm, class $\mathcal {C}$ includes two novel GC algorithms: the $d$ -Choices GC algorithm, that selects $d$ blocks uniformly at random and erases the block containing the least number of valid pages among the $d$ selected blocks, and the Random++ GC algorithm, that repeatedly selects another block uniformly at random until it finds a block with a lower than average number of valid blocks. Using simulation experiments, we show that the proposed mean field model is highly accurate in predicting the write amplification (for drives with $N=50{,}000$ blocks). We further show that the $d$ -Choices GC algorithm has a write amplification close to that of the Greedy GC algorithm even for small $d$ values, e.g., $d = 10$ , and offers a more attractive trade-off between its simplicity and its performance than the Windowed GC algorithm introduced and analyzed in earlier studies. The Random++ algorithm is shown to be less effective as it is even inferior to the FIFO algorithm when the number of pages $b$ per block is large (e.g., for $b \ge 64$ ).     

Coherent optical writing and reading of the exciton spin state in single quantum dots

We demonstrate a one-to-one correspondence between the polarization state of a light pulse tuned to neutral exciton resonances of single semiconductor quantum dots and the spin state of the exciton that it photogenerates. This is accomplished using two variably polarized and independently tuned picosecond laser pulses. The first "writes" the spin state of the resonantly excited exciton. The second is tuned to biexcitonic resonances, and its absorption is used to "read" the exciton spin state. The absorption of the second pulse depends on its polarization relative to the exciton spin direction. Changes in the exciton spin result in corresponding changes in the intensity of the photoluminescence from the biexciton lines which we monitor, obtaining thus a one-to-one mapping between any point on the Poincaré sphere of the light polarization to a point on the Bloch sphere of the exciton spin.     

Elastic building blocks for confined sheets

We study the behavior of thin elastic sheets that are bent and strained under a weak, smooth confinement. We show that the emerging shapes exhibit the coexistence of two types of domains. A focused-stress patch is subject to a geometric, piecewise-inextensibility constraint, whereas a diffuse-stress region is characterized by a mechanical constraint-the dominance of a single component of the stress tensor. We discuss the implications of our findings for the analysis of elastic sheets under various types of forcing.     

Diamine-catalyzed conjugate addition to acrylate derivatives

Diamines were found to promote catalytic conjugate addition of α-cyano active methine nucleophiles to various acrylate derivatives.     

String kernels and high-quality data set for improved prediction of kinked helices in α-helical membrane proteins

The reasons for distortions from optimal α-helical geometry are widely unknown, but their influences on structural changes of proteins are significant. Hence, their prediction is a crucial problem in structural bioinformatics. For the particular case of kink prediction, we generated a data set of 132 membrane proteins containing 1014 manually labeled helices and examined the environment of kinks. Our sequence analysis confirms the great relevance of proline and reveals disproportionately high occurrences of glycine and serine at kink positions. The structural analysis shows significantly different solvent accessible surface area mean values for kinked and nonkinked helices. More important, we used this data set to validate string kernels for support vector machines as a new kink prediction method. Applying the new predictor, about 80% of all helices could be correctly predicted as kinked or nonkinked even when focusing on small helical fragments. The results exceed recently reported accuracies of alternative approaches and are a consequence of both the method and the data set.     

Raman spectra of long chain hydrocarbons: anharmonic calculations, experiment and implications for imaging of biomembranes

First-principles anharmonic vibrational calculations are carried out for the Raman spectrum of the C-H stretching bands in dodecane, and for the C-D bands in the deuterated molecule. The calculations use the Vibrational Self-Consistent Field (VSCF) algorithm. The results are compared with liquid-state experiments, after smoothing the isolated-molecule sharp-line computed spectra. Very good agreement between the computed and experimental results is found for the two systems. The combined theoretical and experimental results provide insights into the spectrum, elucidating the roles of symmetric and asymmetric CH(3) and CH(2) hydrogenic stretches. This is expected to be very useful for the interpretation of spectra of long-chain hydrocarbons. The results show that anharmonic effects on the spectrum are large. On the other hand, vibrational degeneracy effects seem to be rather modest at the resolution of the experiments. The degeneracy effects may have more pronounced manifestations in higher-resolution experiments. The results show that first-principles anharmonic vibrational calculations for hydrocarbons are feasible, in good agreement with experiment, opening the way for applications to many similar systems. The results may be useful for the analysis of CARS imaging of lipids, for which dodecane is a representative molecule. It is suggested that first-principles vibrational calculations may be useful also for CARS imaging of other systems.     

Derivatization-independent cholesterol analysis in crude lipid extracts by liquid chromatography/mass spectrometry: applications to a rabbit model for atherosclerosis

Direct measurement of various sterols in crude lipid extracts in a single experiment from limited biological samples is challenging. Current mass spectrometry (MS) based approaches usually require chemical derivatization before subjecting to MS analysis. Here, we present a derivatization-independent method for analyzing various sterols, including cholesterol and its congeners, using liquid chromatography and atmospheric pressure chemical ionization mass spectrometry. Based on the specific tandem mass spectrometry pattern of cholesterol, multiple reaction monitoring (MRM) transitions were used to quantify free cholesterol and its fatty acyl esters. Several cholesterol oxidation products could also be measured using the upfront liquid chromatography separation and specific MRM transitions. The method was validated alongside established enzymatic assays in measuring total cholesterol. As a proof of concept, we analyzed plasma sterols in rabbits administrated with a high cholesterol diet (HCD) which is a classical atherosclerotic model. Free cholesterol, cholesterol esters, 7-hydroxycholesterol, and 7-ketocholesterol were elevated in plasma of rabbits on HCD. This method could also serve as an excellent tool for quantitative analysis of other sterols such as ergosterol and sitosterol in other organisms beside mammalian. In Saccharomyces cerevisiae, our results indicated dramatic increases of the ratio of ergosterol esters to free ergosterol in both yeh2Δ and tgl1Δ cells, which are consistent with the function of the respective enzymes.