共查询到20条相似文献，搜索用时 31 毫秒
1.
Giese RF 《Science (New York, N.Y.)》1971,172(3980):263-264
The electrostatic energy of the 2M(1) muscovite structure, KAl(2)(Si(3)Al)- O(10)(OH)(2), has been calculated as a function of the orientation of the hydroxyl group (O-H distance = 0.97 angstrom). The minimum in the electrostatic energy occurs when the OH bond makes an angle of 18 degrees with the cleavage plane and an angle of 31 degrees with the b-axis (in the a-b plane), which is 2.5 degrees away from the orientation of the transition moment as determined from infrared measurements on single crystals. If the K+ ion is excluded from the calculation, the O-H bond makes an angle of 53 degrees with the cleavage plane. This indicates the strong influence that the interlayer cation exerts on the hydroxyl hydrogen in mica structures. 相似文献
2.
Past efforts to achieve selective bond scission by vibrational excitation have been thwarted by energy thermalization. Here we report resonant photodesorption of hydrogen from a Si(111) surface using tunable infrared radiation. The wavelength dependence of the desorption yield peaks at 0.26 electron volt: the energy of the Si-H vibrational stretch mode. The desorption yield is quadratic in the infrared intensity. A strong H/D isotope effect rules out thermal desorption mechanisms, and electronic effects are not applicable in this low-energy regime. A molecular mechanism accounting for the desorption event remains elusive. 相似文献
3.
Subbaraman R Tripkovic D Strmcnik D Chang KC Uchimura M Paulikas AP Stamenkovic V Markovic NM 《Science (New York, N.Y.)》2011,334(6060):1256-1260
Improving the sluggish kinetics for the electrochemical reduction of water to molecular hydrogen in alkaline environments is one key to reducing the high overpotentials and associated energy losses in water-alkali and chlor-alkali electrolyzers. We found that a controlled arrangement of nanometer-scale Ni(OH)(2) clusters on platinum electrode surfaces manifests a factor of 8 activity increase in catalyzing the hydrogen evolution reaction relative to state-of-the-art metal and metal-oxide catalysts. In a bifunctional effect, the edges of the Ni(OH)(2) clusters promoted the dissociation of water and the production of hydrogen intermediates that then adsorbed on the nearby Pt surfaces and recombined into molecular hydrogen. The generation of these hydrogen intermediates could be further enhanced via Li(+)-induced destabilization of the HO-H bond, resulting in a factor of 10 total increase in activity. 相似文献
4.
Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur. 相似文献
5.
Direct addition of O-H radicals at room temperature to the carbon No.5 of the uracil ring has been proved by measurement of the proton hyperfine structure in the electron spin resonance of the resulting uracil + O-H radicals. Upon addition of the OH, the H originally bound to carbon No. 5 shifts to No. 6, thus forming a methylene group at carbon No. 6, with the two protons having equivalent coupling of 28 gauss. The spin density on carbon No. 5 is O.64. The radicals were produced when powdered samples of uracil were subjected to a low-velocity beam of O-H radicals coming from either hydrogen peroxide or water vapor under reduced pressure and subjected to an electric discharge. 相似文献
6.
Geissler PL Dellago C Chandler D Hutter J Parrinello M 《Science (New York, N.Y.)》2001,291(5511):2121-2124
The dissociation of a water molecule in liquid water is the fundamental event in acid-base chemistry, determining the pH of water. Because of the short time scales and microscopic length scales involved, the dynamics of this autoionization have not been directly probed by experiment. Here, the autoionization mechanism is revealed by sampling and analyzing ab initio molecular dynamics trajectories. We identify the rare fluctuations in solvation energies that destabilize an oxygen-hydrogen bond. Through the transfer of protons along a hydrogen bond "wire," the nascent ions separate by three or more neighbors. If the hydrogen bond wire connecting the two ions is subsequently broken, a metastable charge-separated state is visited. The ions may then diffuse to large separations. If, however, the hydrogen bond wire remains unbroken, the ions recombine rapidly. Because of their concomitant large electric fields, the transient ionic species produced in this case may provide an experimentally detectable signal of the dynamics we report. 相似文献
7.
AF Goncharov VV Struzhkin MS Somayazulu RJ Hemley HK Mao 《Science (New York, N.Y.)》1996,273(5272):218-220
Protonated and deuterated ices (H2O and D2O) compressed to a maximum pressure of 210 gigapascals at 85 to 300 kelvin exhibit a phase transition at 60 gigapascals in H2O ice (70 gigapascals in D2O ice) on the basis of their infrared reflectance spectra determined with synchrotron radiation. The transition is characterized by soft-mode behavior of the nu3 O-H or O-D stretch below the transition, followed by a hardening (positive pressure shift) above it. This behavior is interpreted as the transformation of ice phase VII to a structure with symmetric hydrogen bonds. The spectroscopic features of the phase persisted to the maximum pressures (210 gigapascals) of the measurements, although changes in vibrational mode coupling were observed at 150 to 160 gigapascals. 相似文献
8.
Suzuki S Green PG Bumgarner RE Dasgupta S Goddard WA Blake GA 《Science (New York, N.Y.)》1992,257(5072):942-945
Fully rotationally resolved spectra of three isotopic species of 1:1 clusters of benzene with water (H(2)O, D(2)O, and HDO) were fit to yield moments of inertia that demonstrate unambiguously that water is positioned above the benzene plane in nearly free internal rotation with both hydrogen atoms pointing toward the pi cloud. Ab initio calculations (MP2 level of electron correlation and 6-31 G(**) basis set with basis set superposition error corrections) predict a binding energy D(e) greater, similar 1.78 kilocalories per mole. In both the experimental and theoretical structures, water is situated nearly 1 angstrom within the van der Waals contacts of the monomers, a clear manifestation of hydrogen bond formation in this simple model of aqueous-pi electron interactions. 相似文献
9.
Energy redistribution, including the many phonon-assisted and electronically assisted energy-exchange processes at a gas-metal interface, can hamper vibrationally mediated selectivity in chemical reactions. We establish that these limitations do not prevent bond-selective control of a heterogeneously catalyzed reaction. State-resolved gas-surface scattering measurements show that the nu1 C-H stretch vibration in trideuteromethane (CHD3) selectively activates C-H bond cleavage on a Ni(111) surface. Isotope-resolved detection reveals a CD3:CHD2 product ratio > 30:1, which contrasts with the 1:3 ratio for an isoenergetic ensemble of CHD3 whose vibrations are statistically populated. Recent studies of vibrational energy redistribution in the gas and condensed phases suggest that other gas-surface reactions with similar vibrational energy flow dynamics might also be candidates for such bond-selective control. 相似文献
10.
Cruzan JD Braly LB Liu K Brown MG Loeser JG Saykally RJ 《Science (New York, N.Y.)》1996,271(5245):59-62
Measurement of the far-infrared vibration-rotation tunneling spectrum of the perdeuterated water tetramer is described. Precisely determined rotational constants and relative intensity measurements indicate a cyclic quasi-planar minimum energy structure, which is in agreement with recent ab initio calculations. The O-O separation deduced from the data indicates a rapid exponential convergence to the ordered bulk value with increasing cluster size. Observed quantum tunneling splittings are interpreted in terms of hydrogen bond rearrangements connecting two degenerate structures. 相似文献
11.
Smith JD Cappa CD Wilson KR Messer BM Cohen RC Saykally RJ 《Science (New York, N.Y.)》2004,306(5697):851-853
A strong temperature dependence of oxygen K-edge x-ray absorption fine structure features was observed for supercooled and normal liquid water droplets prepared from the breakup of a liquid microjet. Analysis of the data over the temperature range 251 to 288 kelvin (-22 degrees to +15 degrees C) yields a value of 1.5 +/- 0.5 kilocalories per mole for the average thermal energy required to effect an observable rearrangement between the fully coordinated ("ice-like") and distorted ("broken-donor") local hydrogen-bonding configurations responsible for the pre-edge and post-edge features, respectively. This energy equals the latent heat of melting of ice with hexagonal symmetry (ice Ih) and is consistent with the distribution of hydrogen bond strengths obtained for the "overstructured" ST2 model of water. 相似文献
12.
Fecko CJ Eaves JD Loparo JJ Tokmakoff A Geissler PL 《Science (New York, N.Y.)》2003,301(5640):1698-1702
We investigated rearrangements of the hydrogen-bond network in water by measuring fluctuations in the OH-stretching frequency of HOD in liquid D2O with femtosecond infrared spectroscopy. Using simulations of an atomistic model of water, we relate these frequency fluctuations to intermolecular dynamics. The model reveals that OH frequency shifts arise from changes in the molecular electric field that acts on the proton. At short times, vibrational dephasing reflects an underdamped oscillation of the hydrogen bond with a period of 170 femtoseconds. At longer times, vibrational correlations decay on a 1.2-picosecond time scale because of collective structural reorganizations. 相似文献
13.
Evaluation of intrinsic binding energy from a hydrogen bonding group in an enzyme inhibitor 总被引：1，自引：0，他引：1
This and two accompanying reports describe the intrinsic binding energy derived from a single hydrogen bond between an inhibitor and an enzyme. The results were obtained by comparing matched pairs of inhibitors of the zinc endopeptidase thermolysin that bind to the enzyme in an essentially identical manner but differ in the presence or absence of a specific hydrogen bond. This report describes five phosphorus-containing analogs of the peptides carbobenzoxy-Gly-Leu-X, in which the Gly-Leu peptide linkage is replaced with a phosphonate ester (-PO2(-)-O-). Values for the inhibition constants of these inhibitors show a direct relation with those of the corresponding phosphonamidate analogs (-PO2(-)-NH- in place of the Gly-Leu peptide moiety), which have been characterized previously as transition state analogs. However, each phosphonate ester is bound about 840 times more weakly than the analogous phosphonamidate, reflecting the loss of 4.0 +/- 0.1 kilocalories per mole in binding energy. From these results and the crystallographic analysis in the next report, it can be inferred that the value of 4.0 kilocalories per mole represents the intrinsic binding energy arising from a highly specific hydrogen binding interaction. 相似文献
14.
Polymer membranes are attractive for molecular-scale separations such as hydrogen purification because of inherently low energy requirements. However, membrane materials with outstanding hydrogen separation performance in feed streams containing high-pressure carbon dioxide and impurities such as hydrogen sulfide and water are not available. We report highly permeable, reverse-selective membrane materials for hydrogen purification, as exemplified by molecularly engineered, highly branched, cross-linked poly(ethylene oxide). In contrast to the performance of conventional materials, we demonstrate that plasticization can be harnessed to improve separation performance. 相似文献
15.
Anesthesia cutoff phenomenon: interfacial hydrogen bonding 总被引：6，自引：0，他引：6
Anesthesia "cutoff" refers to the phenomenon of loss of anesthetic potency in a homologous series of alkanes and their derivatives when their sizes become too large. In this study, hydrogen bonding of 1-alkanol series (ethanol to eicosanol) to dipalmitoyl-L-alpha-phosphatidylcholine (DPPC) was studied by Fourier transform infrared spectroscopy (FTIR) in DPPC-D2O-in-CCl4 reversed micelles. The alkanols formed hydrogen bonds with the phosphate moiety of DPPC and released the DPPC-bound deuterated water, evidenced by increases in the bound O-H stretching signal of the alkanol-DPPC complex and also in the free O-D stretching band of unbound D2O. These effects increased according to the elongation of the carbon chain of 1-alkanols from ethanol (C2) to 1-decanol (C10), but suddenly almost disappeared at 1-tetradecanol (C14). Anesthetic potencies of these alkanols, estimated by the activity of brine shrimps, were linearly related to hydrogen bond-breaking activities below C10 and agreed with the FTIR data in the cutoff at C10. 相似文献
16.
Fermi resonance was observed between the OH stretch and the overtone of the OH bending modes of HDO molecules contaminated in phase VII of D(2)O ice over the pressure range from 17 to 30 gigapascals. An anharmonic coupling constant, which is related to the potential energy surface on which hydrogen-bonded protons oscillate, was found to range around 50 wave numbers through the resonant pressure range. Its experimentally obtained magnitude and pressure-insensitive behavior will be useful for theoretical studies of the potential energy surface and hence of the nature of hydrogen bonding in ice. 相似文献
17.
The relative influence of thermal and quantum fluctuations on the proton transfer properties of the charged water complexes H5O2+ and H3O2- was investigated with the use of ab initio techniques. These small systems can be considered as prototypical representatives of strong and intermediate-strength hydrogen bonds. The shared proton in the strongly hydrogen bonded H5O2+ behaved in an essentially classical manner, whereas in the H3O2- low-barrier hydrogen bond, quantum zero-point motion played a crucial role even at room temperature. This behavior can be traced back to a small difference in the oxygen-oxygen separation and hence to the strength of the hydrogen bond. 相似文献
18.
Glusker JP Zacharias DE Whalen DL Friedman S Pohl TM 《Science (New York, N.Y.)》1982,215(4533):695-696
The existence of an internal hydrogen bond in a compound representative of a syn diol epoxide (a possible intermediate in chemical carcinogenesis by certain polycyclic aromatic hydrocarbons) has been demonstrated by x-ray crystallographic and nuclear magnetic resonance studies. This internal hydrogen bond was found in 3,4-epoxy-2-methyl-1,2,3,4-tetrahydro-1-naphthol and was shown to persist in dioxane-water solutions containing up to 80 mole percent water. In this structure, the 1-hydroxy and 2-methyl groups are shown to occupy axial positions. In the anti diol epoxide, which has no internal hydrogen bond, analogous groups are equatorial. Crystals of the compound were unstable in the x-ray beam while the data were being collected (even at low temperatures), presumably as a result of decomposition. 相似文献
19.
The membrane microstructures and the mechanism of two coated ureas formed through solidliquid reaction were observed by scanning electron microscope and infrared spectra, the relation of the structural characteristics with the nitrogen release feature was also discussed by combining with nitrogen dissolution in water. The results showed that the membranes were made of solid particles tightly connected to each other and were piled up layer by layer through liquid glue. Porosity and aperture of membrane were determined by compactness of piled layers and the particles in a single layer and also related to the characteristics of coating materials. Research of the infrared spectra of membrane, made of a solid powder and a liquid glue, proved that O-H on the solid surface was bonded with the double bond of the liquid glue, thus forming membrane and keeping it stable. It was found that the two coated ureas showed obvious differences in nitrogen releasing due to their membrane structures, the porosity and aperture of membrane were the critical factors for nitrogen releasing. 相似文献
20.
以乙酸木素、二次纤维为原料添加异氰酸酯及聚乙二醇400,制备聚氨酯纸基复合材料.聚氨酯处理使纸张纤维间的氢键连接转变为共价键连接,从而使复合材料的抗张强度、环压强度、抗水性质均有很大程度提高;并且,随着预聚体中乙酸木素含量的提高,复合材料的强度指标均先上升后下降,吸水率先降低后提高. 相似文献