A multinuclear NMR and quantum chemical study of solid trimethylammonium chloride

The solid salt, trimethylammonium chloride (TMAC), is investigated by a combination of NMR spectroscopic techniques and quantum chemical calculations. Chemical shift and nuclear quadrupolar interaction parameters have been measured for 35Cl, 1H/2H, and 15N/14N. These parameters have also been calculated as a function of the hydrogen position in the N\u2022\u2022\u2022H\u2022\u2022\u2022Cl fragment. Overall, the measured parameters are consistent with a structure in which the hydrogen is completely transferred to the nitrogen (i.e., N\u2013H\u2022\u2022\u2022Cl). The high hydrogen chemical shift (10.9 ppm by 2H CP/MAS) and relatively small deuterium quadrupolar coupling constant (127 kHz) indicate a moderately strong N\u2013H\u2022\u2022\u2022Cl hydrogen bond. A pronounced deuterium isotope effect on the 35Cl quadrupolar coupling constant is observed.Peer reviewed: YesNRC publication: Ye

The source counts of submillimetre galaxies detected at 1.1 mm

The source counts of galaxies discovered at sub-millimetre and millimetre wavelengths provide important information on the evolution of infrared-bright galaxies. We combine the data from six blank-field surveys carried out at 1.1 mm with AzTEC, totalling 1.6 square degrees in area with root-mean-square depths ranging from 0.4 to 1.7 mJy, and derive the strongest constraints to date on the 1.1 mm source counts at flux densities S(1100) = 1-12 mJy. Using additional data from the AzTEC Cluster Environment Survey to extend the counts to S(1100) ~ 20 mJy, we see tentative evidence for an enhancement relative to the exponential drop in the counts at S(1100) ~ 13 mJy and a smooth connection to the bright source counts at >20 mJy measured by the South Pole Telescope; this excess may be due to strong lensing effects. We compare these counts to predictions from several semi-analytical and phenomenological models and find that for most the agreement is quite good at flux densities > 4 mJy; however, we find significant discrepancies (>3sigma) between the models and the observed 1.1 mm counts at lower flux densities, and none of them are consistent with the observed turnover in the Euclidean-normalised counts at S(1100) < 2 mJy. Our new results therefore may require modifications to existing evolutionary models for low luminosity galaxies. Alternatively, the discrepancy between the measured counts at the faint end and predictions from phenomenological models could arise from limited knowledge of the spectral energy distributions of faint galaxies in the local Universe.Comment: 16 pages, 3 figures, 4 tables; accepted for publication in MNRA

Physiological Correlates of Volunteering

We review research on physiological correlates of volunteering, a neglected but promising research field. Some of these correlates seem to be causal factors influencing volunteering. Volunteers tend to have better physical health, both self-reported and expert-assessed, better mental health, and perform better on cognitive tasks. Research thus far has rarely examined neurological, neurochemical, hormonal, and genetic correlates of volunteering to any significant extent, especially controlling for other factors as potential confounds. Evolutionary theory and behavioral genetic research suggest the importance of such physiological factors in humans. Basically, many aspects of social relationships and social activities have effects on health (e.g., Newman and Roberts 2013; Uchino 2004), as the widely used biopsychosocial (BPS) model suggests (Institute of Medicine 2001). Studies of formal volunteering (FV), charitable giving, and altruistic behavior suggest that physiological characteristics are related to volunteering, including specific genes (such as oxytocin receptor [OXTR] genes, Arginine vasopressin receptor [AVPR] genes, dopamine D4 receptor [DRD4] genes, and 5-HTTLPR). We recommend that future research on physiological factors be extended to non-Western populations, focusing specifically on volunteering, and differentiating between different forms and types of volunteering and civic participation

Lawson criterion for ignition exceeded in an inertial fusion experiment

For more than half a century, researchers around the world have been engaged in attempts to achieve fusion ignition as a proof of principle of various fusion concepts. Following the Lawson criterion, an ignited plasma is one where the fusion heating power is high enough to overcome all the physical processes that cool the fusion plasma, creating a positive thermodynamic feedback loop with rapidly increasing temperature. In inertially confined fusion, ignition is a state where the fusion plasma can begin "burn propagation" into surrounding cold fuel, enabling the possibility of high energy gain. While "scientific breakeven" (i.e., unity target gain) has not yet been achieved (here target gain is 0.72, 1.37 MJ of fusion for 1.92 MJ of laser energy), this Letter reports the first controlled fusion experiment, using laser indirect drive, on the National Ignition Facility to produce capsule gain (here 5.8) and reach ignition by nine different formulations of the Lawson criterion

Structure and dynamics of ND\u2083BF\u2083 in the solid and gas phases : a combined NMR, neutron diffraction, and Ab initio study

The decrease in D-->A bond lengths, previously reported for some Lewis acid/base complexes, in going from the gas to the solid phases is investigated by obtaining an accurate crystal structure of solid ND(3)BF(3) by powder neutron diffraction. The B-N internuclear distance is 1.554(3) A, 0.118 A shorter than the most recent gas-phase microwave value and 0.121 A shorter than the single molecule geometry optimized (1.672 A, CISD/6-311++G(d,p)) bond length. The crystal structure also shows N-D.F-B hydrogen bonds. The effects of this change in structure and of intermolecular hydrogen-bonding on nuclear magnetic shielding (i.e., chemical shifts) and the nuclear quadrupolar coupling constants (QCC) are investigated by ab initio molecular orbital and density functional theory calculations. These calculations show that the nitrogen ((15)N and (14)N) and boron ((11)B and (10)B) chemical shifts should be rather insensitive to changes in r(BN) and that the concomitant changes in molecular structure. Calculations on hydrogen-bonded clusters, based on the crystal structure, indicate that H-bonding should also have very little effect on the chemical shifts. On the other hand, the (11)B and (14)N QCCs show large changes because of both effects. An analysis of the (10)B[(19)F] line shape in solid ND(3)(10)BF(3) yields a (11)B QCC of +/-0.130 MHz. This is reasonably close an earlier value of +/-0.080 MHz and the value of +/-0.050 MHz calculated for a [NH(3)BF(3)](4) cluster. The gas-phase value is 1.20 MHz. Temperature-dependent deuterium T(1) measurements yield an activation energy for rotation of the ND(3) group in solid ND(3)BF(3) of 9.5 +/- 0.1 kJ/mol. Simulations of the temperature-dependent T(1) anisotropy gave an E(a) of 9.5 +/- 0.2 kJ/mol and a preexponential factor, A, of 3.0 +/- 0.1 x 10(12) s(-)(1). Our calculated value for a [NH(3)BF(3)](4) cluster is 16.4 kJ/mol. Both are much higher than the previous value of 3.9 kJ/mol, from solid-state proton T(1) measurements.Peer reviewed: YesNRC publication: Ye

Polymorphism, structure, guest conformation, and dynamics in the inclusion compound of 1,2-dichloroethane with tris(5-acetyl-3-thienyl) methane : a combined single crystal and powder X-ray diffraction, 13C CP/MAS, and 2H NMR study

Various physicochemical characterization techniques were used to study the structure and guest dynamics of the 1,2-dichloroethane/tris (5-acetyl-3-thienyl) methane (TATM) inclusion compound. This complex was observed to crystallize in two forms, a triclinic P-1 structure and a less usual monoclinic P21/c form. The X-ray structures indicate that the TATM molecules form "bottleneck" channels parallel to the crystallographic c axis in both forms and that the guests exist exclusively in the trans form. Solid-state deuterium NMR spectroscopy was used to study the dynamics of the 1,2-dichloroethane-d4 guest in the triclinic form. The simplest model consistent with the experimental NMR spectra was based on internal rotation about the C-C bond (a trans/gauche conformational equilibrium). As this was not consistent with the X-ray structure, another model was developed where the trans conformer performs 180 flips about an axis through the center of symmetry of the guest and perpendicular to the Cl-C-C-Cl plane. The important point to be taken from this work is that complementary methods are often necessary to discriminate between motional models based on a single technique, and that the simplest model is not necessarily correct.Peer reviewed: YesNRC publication: Ye