Study of statics and dynamics of hydrogen bonds using neutron scattering

The various observables which can be derived using neutron scattering in hydrogen-bonded systems are reviewed and a sample of experiments dealing with those observables is also presented. The relevance of the non-localized behaviour of the hydrogen wave function is also discussed.     

Hydrogen bonding in potassium hydrogen maleate and some simple derivatives studied by inelastic neutron scattering spectroscopy

Inelastic neutron scattering spectra (300–2500 cm^?1) of KH(CHCO₂)₂, KD(CHCO₂)₂, KH(CDCO₂)₂ and KH(CHCO₂ · CClCO₂) have been obtained and the vibrations of the hydrogen bond, with the exception of ν₂(OHO), assigned. This is the first assignment of these vibrations in a centrosymmetric intramolecularly hydrogen bonded complex. ν_as(OHO) was found to be heavily mixed and to give rise to a strong doublet in the INS spectra.     

Hydrogen dynamics in Na3AlH6: a combined density functional theory and quasielastic neutron scattering study

Understanding the elusive catalytic role of titanium-based additives on the reversible hydrogenation of complex hydrides is an essential step toward developing hydrogen storage materials for the transport sector. Improved bulk diffusion of hydrogen is one of the proposed effects of doping sodium alanate with TiCl3, and here we study hydrogen dynamics in doped and undoped Na3AlH6 using a combination of density functional theory calculations and quasielastic neutron scattering. The hydrogen dynamics is found to be vacancy mediated and dominated by localized jump events, whereas long-range bulk diffusion requires significant activation. The fraction of mobile hydrogen is found to be small for both undoped and doped Na3AlH6, even at 350 K, and improved hydrogen diffusion as a result of bulk-substituted titanium is found to be unlikely. We also propose that previously detected low-temperature point defect motion in sodium alanate could result from vacancy-mediated sodium diffusion.     

Hydrogen motions in the alpha-relaxation regime of poly(vinyl ethylene): a molecular dynamics simulation and neutron scattering study

The hydrogen motion in poly(vinyl ethylene) (1,2-polybutadiene) in the alpha-relaxation regime has been studied by combining neutron spin echo (NSE) measurements on a fully protonated sample and fully atomistic molecular dynamics simulations. The almost perfect agreement between experiment and simulation results validates the simulated cell. A crossover from Gaussian to non-Gaussian behavior is observed for the intermediate scattering function obtained from both NSE measurements and simulations. This crossover takes place at unusually low Q values, well below the first maximum of the static structure factor. Such anomalous deviation from Gaussian behavior can be explained by the intrinsic dynamic heterogeneity arising from the differences in the dynamics of the different protons in this system. Side group hydrogens show a markedly higher mobility than main chain protons. Taking advantage of the simulations we have investigated the dynamic features of all different types of hydrogens in the sample. Considering each kind of proton in an isolated way, deviations from Gaussian behavior are also found. These can be rationalized in the framework of a simple picture based on the existence of a distribution of discrete jumps underlying the atomic motions in the alpha process.     

Determination of a hydroxyl conformation in aqueous xylose using neutron scattering and molecular dynamics

Recently, it was shown using structural neutron diffraction with isotopic substitutions (NDIS) measurements, combined with molecular dynamics simulations, that in an aqueous solution of D-xylose the hydroxyl group on the C4 position does not significantly occupy the position trans to the H4 atom. Here, a similar combination of NDIS and MD studies is described which uses D-xylose deuterated at the C5 position to further characterize this hydroxyl conformation as being trans to the C5 atom, as predicted by constrained MD simulations, confirming the previous study.     

Interpretation of the hydrogen anomaly in neutron and electron compton scattering

In Compton scattering with neutrons in the energy range 20–120 eV, it has been observed that the relative H/M cross sections in a variety of H‐containing materials are 20–40% lower than expected from the composition ratio H/M (M being a heavier element in the same compound). The same phenomenon has also been observed in Compton scattering with electrons of 2 and 20 keV energy. There is, at present, no consensus about the reason for these anomalies. In this theory, they are explained as a result of interference when the scattering particle interacts with more than one hydrogen nucleus. The coherence volume of the actual setup, which limits the number of interfering particles, is therefore an important parameter. It is shown here that the large zero‐point motion of the hydrogen nuclei leads to reductions in the scattering intensity from interfering pairs. Coherence is preserved over the sub‐fs scattering times relevant for this process, even in the condensed systems studied. It is gradually lost when the scattering time is increased, which happens when the neutron energy is reduced (as reflected in lower anomalies for smaller scattering angles). Explicit expressions for the decoherence effect are presented and compared with experimental observation for a selection of observed H‐ and D‐containing systems. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Electron screening in low energy scattering of muonic hydrogen on hydrogen atoms

Electron screening corrections to the cross sections for low energy scattering of muonic hydrogen on hydrogen atoms are calculated. It is shown that the presence of the electron influences considerably the elastic cross sections at collision energies below 1 eV. This influence is relatively small for the spin-flip and isotopic exchange processes.     

A single crystal and polycrystalline study of potassium hydrogen malonate using inelastic neutron scattering

The incoherent ineleastic neutron scattering spectra of single and polycrystal samples of potassium hydrogen (deuterium) malonate have been obtained. These spectra have been assigned in concordance with optical spectra except for the location of the antisymmetric hydrogen bond stretch ν_as(OHO) which we observe at 470 cm⁻¹. The corresponding band in the spectrum of the deuterated sample occurs at 411 cm⁻¹. The CO₂ scissoring mode was also observed with significant intensity. These results are interpreted as a mixing of the two modes. This explains the rotation of ν_as(OHO) displacement vector. This vector lies, not along an O ⋯ O direction, but along a C ⋯ C direction.     

Phenylene ring dynamics in bisphenol-A-polysulfone by neutron scattering

We have investigated the dynamics of phenylene rings in a glassy polysulfone (bisphenol-A-polysulfone) by means of quasielastic neutron scattering. Nowadays it is well known that these molecular motions are directly connected with the mechanical properties of engineering thermoplastics in general. The particular system investigated by us has the advantage that by selective deuteration of the methyl groups, the neutron scattering measured is dominated by the incoherent contribution from the protons in the phenylene rings. In this way, the dynamics of such molecular groups can be experimentally isolated. Two different types of neutron spectrometers: time of flight and backscattering, were used in order to cover a wide dynamic range, which extends from microscopic (10(-13) s) to mesoscopic (10(-9) s) times. Moreover, neutron diffraction experiments with polarization analysis were also carried out in order to characterize the structural features of the sample investigated. Fast oscillations of increasing amplitude with temperature and pi-flips are identified for phenylene rings motions. Due to the structural disorder characteristic of the amorphous state, both molecular motions display a broad distribution of relaxation times, which spreads over several orders of magnitude. Based on the results obtained, we propose a model for phenylene rings dynamics, which combines the two kinds of molecular motions identified. This model nicely describes the neutron scattering results in the whole dynamic range investigated.     

An inelastic neutron scattering study of hydrogen bonding in potassium hydrogen dichloromaleate

The inelastic neutron scattering (INS) spectrum (350–2000 cm^?1) of potassium hydrogen dichloromaleate (solid slate) has been obtained. Two of the normal modes of vibration of the hydrogen bond [γ(OHO) and δ(OHO)] were observed and assigned. No INS band v_as(OHO) was observed in the region 500–1300 cm^?1. This conflicts with expectations from infrared data.     

Effect of temperature and pressure on the structure, dynamics, and hydrogen bond properties of liquid N-methylacetamide: a molecular dynamics study

The structure and dynamical properties of liquid N-methylacetamides (NMA) are calculated at five different temperatures and at four different pressures using classical molecular dynamics simulations. Our results are analyzed in terms of pressure-induced changes in structural properties by investigating the radial distribution functions of different atoms in NMA molecule. It is found that the first peak and also the second peak of C-O and N-H are well defined even at higher temperature and pressure. It is also observed that the number of hydrogen bonds increase with application of pressure at a given temperature. On the other hand, the calculated hydrogen bond energy (E(HB)) shows that the stability of hydrogen bond decreases with increasing of pressure and temperature. Various dynamical properties associated with translational and rotational motion of neat NMA are calculated and the self-diffusion coefficient of NMA is found to be in excellent agreement with the experiment and the behavior is non-Arrhenius at low temperatures with application of pressures. The single particle orientational relaxation time for dipole vector and N-C vector are also calculated and it is found that the orientational relaxation time follows Arrhenius behavior with a variation of temperature and pressure.     

Molecular dynamics of glucose in solution: a quasielastic neutron scattering study

The molecular dynamics of glucose dissolved in heavy water have been investigated at 280 K by the technique of quasielastic neutron scattering. The scattering was described by a dynamic structure factor that accounts for decoupled diffusive jumps and free rotational motions of the glucose molecules. With increasing glucose concentration, the diffusion constant decreases by a factor five and the time between jumps increases considerably. Our observations validate theoretical predictions concerning the impact of concentration on the environment of a glucose molecule and the formation of cages made by neighboring glucose molecules at higher concentrations.     

Water dynamics in graphite oxide investigated with neutron scattering

Graphite oxide is an inorganic multilayer system that preserves the layered structure of graphite but not the conjugated bond structure. In the past few years, detailed studies of the static structure of graphite oxide were carried out. This was mainly done by NMR investigations and led to a new structural model of graphite oxide. The layer distance of graphite oxide increases with increasing humidity level, giving rise to different spacings of the carbon layers in the range from 6 to 12 A. As a consequence, different types of motions of water and functional groups appear. Information about the mobility of the water molecules is not yet complete but is crucial for the understanding of the structure of the carbon layers as well as the intercalation process. In this paper, the hydration- and temperature-dependent dynamic behavior of graphite oxide will be investigated by quasielastic neutron scattering using the time-of-flight spectrometer NEAT at the Hahn-Meitner-Institut Berlin. The character of the embedded water does not change over a wide range of hydration levels. Especially the interlayer water remains tightly bound and does not show any translational motion. In samples with excess water, however, the water is also distributed in noninterlayer voids, leading to the observation of additional motions of bulklike or confined water. The dynamic behavior of hydrated graphite oxide can be described by a consistent model that combines two two-site jump motions for the motions of the water molecules and the motions of OH groups.     

Evaluation of the individual hydrogen bonding energies in N-methylacetamide chains

The individual hydrogen bonding energies in N-methylacetamide chains were evaluated at the MP2/6-31+G** level including BSSE correction and at the B3LYP/6-311++G(3df,2pd) level including BSSE and van der Waals correction. The calculation results indicate that compared with MP2 results, B3LYP calculations without van der Waals correction underestimate the individual hydrogen bonding energies about 5.4 kJ mol^?1 for both the terminal and central hydrogen bonds, whereas B3LYP calculations with van der Waals correction produce almost the same individual hydrogen bonding energies as MP2 does for those terminal hydrogen bonds, but still underestimate the individual hydrogen bonding energies about 2.5 kJ mol^?1 for the hydrogen bonds near the center. Our calculation results show that the individual hydrogen bonding energy becomes more negative (more attractive) as the chain becomes longer and that the hydrogen bonds close to the interior of the chain are stronger than those near the ends. The weakest individual hydrogen bonding energy is about ?29.0 kJ mol^?1 found in the dimer, whereas with the growth of the N-methylacetamide chain the individual hydrogen bonding energy was estimated to be as large as ?62.5 kJ mol^?1 found in the N-methylacetamide decamer, showing that there is a significant hydrogen bond cooperative effect in N-methylacetamide chains. The natural bond orbital analysis indicates that a stronger hydrogen bond corresponds to a larger positive charge for the H atom and a larger negative charge for the O atom in the N-H?O=C bond, corresponds to a stronger second-order stabilization energy between the oxygen lone pair and the N-H antibonding orbital, and corresponds to more charge transfer between the hydrogen bonded donor and acceptor molecules.     

Neutron scattering by hydrogen in cold neutron prompt gamma-activation analysis

The effects of neutron scattering by hydrogen within targets for cold neutron prompt -ray activation analysis (CNPGAA) have been characterized. For most targets studied, the probability for neutron absorption, and hence CNPGAA sensitivities (counts·s^–1·mg^–1), decrease with increasing H content and with target thickness. Comparisons with results from thermal neutron PGAA indicate that the effects of cold neutron scattering differ from those of thermal neutron scattering. CNPGAA sensitivities for l/v nuclides show similar sensitivity decreases, while Sm sensitivities show smaller decreases.     

Structure and hydrogen bonding in neat N-methylacetamide: classical molecular dynamics and Raman spectroscopy studies of a liquid of peptidic fragments

The results of classical molecular dynamics (MD) simulations and Raman spectroscopy studies of neat liquid N-methylacetamide (NMA), the simplest model system relevant to the peptides, are reported as a function of temperature and pressure. The MD simulations predict that near ambient conditions, the molecules form a hydrogen bond network consisting primarily of linear chains. Both the links between molecules within the hydrogen-bonded chains and the associations between chains are stabilized by weak methyl-donated "improper" hydrogen bonds. The three-dimensional structural motifs observed in the liquid show some similarity to protein beta-sheets. The temperature and pressure dependence of the hydrogen bond network, as probed by the mode frequency of the experimentally determined amide-I Raman band, blue shifts on heating and red shifts under compression, respectively, suggesting weakened and enhanced hydrogen bonding in response to temperature and pressure increases. Disruption of the hydrogen-bonding network is clearly observed in the simulation data as temperature is increased, whereas the improper hydrogen bonding is enhanced under compression to reduce the energetic cost of increasing the packing fraction. Because of the neglect of polarizability in the molecular model, the computed dielectric constant is underestimated compared to the experimental value, indicating that the simulation may underestimate dipolar coupling in the liquid.     

Molecular dynamics simulations of isotope compounds of hydrogen atoms: prospects and progress

In this paper, we proceed with our project of generating an algorithm for molecular dynamics simulations of isotope complexes of hydrogen atoms (Chem. Phys. Lett. 320 (2000) 118). The isotope selection is carried out by forces derived from adiabatic potential energy curves that are obtained within a modified electron mass theory. Arguments are presented in favour of the use of the generalized valence bond electronic wavefunctions. We exemplify with simulations and geometry optimization of H₂ isotopomers and discuss the effects of long-range interactions and electron correlation on the forces.