Vibrational spectra of alkali hydrogen selenites,selenous acid,and their deuterated analogs

The infrared and Raman spectra of alkali hydrogen selenites [(MHSeO₃), where M = Li, Na, K, or Cs], selenous acid (H₂Seo₃), and their deuterated analogs have been recorded and interpreted. The internal mode frequencies observed in sodium hydrogen selenite, selenous acid, and sodium trihydrogen selenite are used to generate general valence force constants for HSeO^?₃ and H₂SeO₃ under the assumption of C_s geometry for each species. Calculations of observed deuterium frequency shifts are made to aid in the assignments of the various internal modes. A low-temperature proton-triggered phase transition is observed in CsHSeO₃ and is confirmed in KHSeO₃. A discussion of the effects of proton order and disorder upon the selenite frequencies is also presented.     

A solid-state NMR method for solution of zeolite crystal structures

Since zeolites are notoriously difficult to prepare as large single crystals, structure determination usually relies on powder X-ray diffraction (XRD). However, structure solution (i.e., deriving an initial structural model) directly from powder XRD data is often very difficult due to the diffraction phase problem and the high degree of overlap between the individual reflections, particularly for materials with the structural complexity of most zeolites. Here, we report a method for structure determination of zeolite crystal structures that combines powder XRD and nuclear magnetic resonance (NMR) spectroscopy in which the crucial step of structure solution is achieved using solid-state (29)Si double-quantum dipolar recoupling NMR, which probes the distance-dependent dipolar interactions between naturally abundant (29)Si nuclei in the zeolite framework. For two purely siliceous zeolite blind test samples, we demonstrate that the NMR data can be combined with the unit cell parameters and space group to solve structural models that refine successfully against the powder XRD data.     

How hydrophobic buckminsterfullerene affects surrounding water structure

The hydrophobic hydration of fullerenes in water is of significant interest as the most common Buckminsterfullerene (C60) is a mesoscale sphere; C60 also has potential in pharmaceutical and nanomaterial applications. We use an all-atom molecular dynamics simulation lasting hundreds of nanoseconds to determine the behavior of a single molecule of C60 in a periodic box of water, and compare this to methane. A C60 molecule does not induce drying at the surface; however, unlike a hard sphere methane, a hard sphere C60 solute does. This is due to a larger number of attractive Lennard-Jones interactions between the carbon atom centers in C60 and the surrounding waters. In these simulations, water is not uniformly arranged but rather adopts a range of orientations in the first hydration shell despite the spherical symmetry of both solutes. There is a clear effect of solute size on the orientation of the first hydration shell waters. There is a large increase in hydrogen-bonding contacts between waters in the C60 first hydration shell. There is also a disruption of hydrogen bonds between waters in the first and second hydration shells. Water molecules in the first hydration shell preferentially create triangular structures that minimize the net water dipole near the surface near both the methane and C60 surface, reducing the total energy of the system. Additionally, in the first and second hydration shells, the water dipoles are ordered to a distance of 8 A from the solute surface. We conclude that, with a diameter of approximately 1 nm, C60 behaves as a large hydrophobic solute.     

Observation of centrifugally driven interchange instabilities in a plasma confined by a magnetic dipole

Centrifugally driven interchange instabilities are observed in a laboratory plasma confined by a dipole magnetic field. The instabilities appear when an equatorial mesh is biased to drive a radial current that causes rapid axisymmetric plasma rotation. The observed instabilities are quasicoherent in the laboratory frame of reference; they have global radial mode structures and low azimuthal mode numbers, and they are modified by the presence of energetic, magnetically confined electrons. Results from a self-consistent nonlinear simulation reproduce the measured mode structures.     

Alkyl inductive effects on molecular ionization potentials—XV n-alkanes

The first ionisation potentials, E_I, of n-alkanes are found to be a linear function of the inductive substituent constants, Σσ_I. The correlation is obtained by considering that a σ-bonding electron is ejected from the most central CC bond in the alkane RR′. The equation for the regression is E_I = 17·19 + 60·2 Σσ_I ± 0·04 eV, with correlation coefficient 0·998. An equation is also deduced relating E_I to the number of carbon atoms, n_c, and hydrogen atoms, n_H, in the n-alkane: E_I = 4·70(n_H - 1)/n_c, from which E_I for polymethylene, (CH₂)_x, is found to be 9·40 eV.     

Thermal history effects and methyl tunneling dynamics in a supramolecular complex of calixarene and para-xylene

The low-temperature structure and dynamics of guest molecules of p-xylene incorporated in the isopropyl-calix[4] arene(2:1) p-xylene complex have been investigated by solid state nuclear magnetic resonance (NMR). Using one-dimensional 1H-decoupled 13C cross-polarization magic-angle-spinning (MAS) NMR and two-dimensional 1H-13C correlation spectroscopy, a full assignment of the 13C and 1H chemical shifts has been made. Using 1H NMR relaxometry, the effects of thermal history on the structure of the system have been investigated. Rapidly cooled samples have 1H spin-lattice relaxation times T1, which at low temperature (T<60 K) are typically two orders of magnitude faster than those observed in annealed samples which have been cooled slowly over many hours. In both forms, the low-temperature relaxation is driven by the dynamics of the weakly hindered methyl rotors of the p-xylene guest. The substantial difference in T1 is attributed in the rapidly cooled sample to disorder in the structure of the complex leading to a wide distribution of correlation times and methyl barrier heights. A comparison of the linewidths and splittings in the high resolution 13C MAS spectra of the two forms provides structural insight into the nature of the disorder. Using 1H field-cycling NMR relaxometry, the methyl dynamics of the p-xylene guest in the annealed sample have been fully characterized. The B-field dependence of the 1H T1 maps out the spectral density from which the correlation times are directly measured. The methyl barrier heights are determined from an analysis of the temperature dependence.     

Theory and applications of supercycled symmetry-based recoupling sequences in solid-state nuclear magnetic resonance

We present the theoretical principles of supercycled symmetry-based recoupling sequences in solid-state magic-angle-spinning NMR. We discuss the construction procedure of the SR26 pulse sequence, which is a particularly robust sequence for double-quantum homonuclear dipole-dipole recoupling. The supercycle removes destructive higher-order average Hamiltonian terms and renders the sequence robust over long time intervals. We demonstrate applications of the SR26 sequence to double-quantum spectroscopy, homonuclear spin counting, and determination of the relative orientations of chemical shift anisotropy tensors.     

Diversity and Popularity in Organizations and Communities

This paper examines social groupings whose structure depends only on the distribution of ability to attract attention. When people&#x2018;s attention is a scarce resource, those individuals who are rated highest by a large number of other individuals will have to ration their attention, resulting in constraints on the social structure of the group. The incidence of popular individuals by that definition reflects the extent to which individuals agree on who their highest-rated colleague is. We propose three basic distributions or ways to generate the matrix of perceived ability so as to yield popularity profiles that can be parametrically adjusted to match observations. We demonstrate that each of these assumption sets leads to a slightly different correlation between the value of the assumption&#x2018;s parameter and the set of observable popularity patterns. Since popularity, in real life, often determines such things as power, centrality, over-utilization and perhaps reduced accessibility, having more realistic ways of representing it is important for modeling and understanding virtual organizations and communities.     

Direct enhancement of nuclear singlet order by dynamic nuclear polarization

Hyperpolarized singlet order is available immediately after dissolution DNP, avoiding need for additional preparation steps. We demonstrate this procedure on a sample of [1,2-(13)C(2)]pyruvic acid.