Zn2+ has a primary hydration sphere of five: IR action spectroscopy and theoretical studies of hydrated Zn2+ complexes in the gas phase

Complexes of Zn(2+)(H(2)O)(n), where n = 6-12, are examined using infrared photodissociation (IRPD) spectroscopy, blackbody infrared radiative dissociation (BIRD), and theory. Geometry optimizations and frequency calculations are performed at the B3LYP/6-311+G(d,p) level along with single point energy calculations for relative energetics at the B3LYP, B3P86, and MP2(full) levels with a 6-311+G(2d,2p) basis set. The IRPD spectrum of Zn(2+)(H(2)O)(8) is most consistent with the calculated spectrum of the five-coordinate MP2(full) ground-state (GS) species. Results from larger complexes also point toward a coordination number of five, although contributions from six-coordinate species cannot be ruled out. For n = 6 and 7, comparisons of the individual IRPD spectra with calculated spectra are less conclusive. However, in combination with the BIRD and laser photodissociation kinetics as well as a comparison to hydrated Cu(2+) and Ca(2+), the presence of five-coordinate species with some contribution from six-coordinate species seems likely. Additionally, the BIRD rate constants show that Zn(2+)(H(2)O)(6) and Zn(2+)(H(2)O)(7) complexes are less stable than Zn(2+)(H(2)O)(8). This trend is consistent with previous work that demonstrates the enthalpic favorability of the charge separation process forming singly charged hydrated metal hydroxide and protonated water complexes versus loss of a water molecule for complexes of n ≤ 7. Overall, these results are most consistent with the lowest-energy structures calculated at the MP2(full) level of theory and disagree with those calculated at B3LYP and B3P86 levels.     

CAN-mediated oxidations for the synthesis of xanthones and related products

Reaction of (2,4,5-trimethoxyphenyl)(2-hydroxyphenyl)methanone with ceric ammonium nitrate furnished the xanthone, 2,3-dimethoxy-9H-xanthen-9-one. Under the same conditions the related (1,4-dimethoxynaphthalen-2-yl)(2-hydroxyphenyl)methanone resulted in the formation of 12a-methoxy-5H-benzo[c]xanthenes 5,7(12aH)-dione. Other examples of this novel transformation are also outlined.     

Impact of plasticizers and tackifiers on the crystallization of isotactic poly(1-butene)

Crystallization of a semi-crystalline polyolefin in the presence of low molecular weight modifiers was quantified by differential scanning calorimetry and optical microscopy. The polyolefin was a commercial grade of isotactic poly(1-butene) (iPB). Two modifiers were used: an oligomeric plasticizer, designated HOAO, which decreased the glass transition temperature (T_g) of the system, and an oligomeric tackifier, designated HOCP, which increased T_g. Binary iPB/modifier blends containing 10% or 20% by weight of HOAO or HOCP were examined to determine how their addition affects T_g, while ternary iPB/HOAO/HOCP blends containing 10% or 20% by weight of total modifier were examined to determine the effects of dilution by using a ratio of HOAO to HOCP that matched the T_g of iPB. The addition of modifier decreased the nucleation rate, spherulitic crystal growth rate, and final crystallinity of each blend. However, only the nucleation rate showed a dependence on the type of modifier, with nucleation retarded more by HOCP than by HOAO. A Hoffman-Weeks analysis of the melting point as a function of crystallization temperature confirmed that the driving force for nucleation was reduced, and that the effect was larger for HOCP. An Avrami analysis of the bulk crystallization kinetics was consistent with these observations, as the Avrami exponents were in the range of 3-4.     

Spectroscopic requirements for ACCURATE, a microwave and infrared-laser occultation satellite mission

The proposed satellite mission ACCURATE consists of a small constellation of satellites in low Earth orbit, combining microwave occultation for thermodynamic state profiling with infrared-laser occultation for greenhouse gas and line-of-sight wind profiling. The mission aims to detect six greenhouse gas molecules with four additional isotopologues (H₂O, CO₂, CH₄, N₂O, O₃, CO, ¹³CO₂, OC¹⁸O, HDO, and H₂¹⁸O) in the upper troposphere and lower stratosphere in the 4000-5000 cm⁻¹ spectral region. Greenhouse gas profiles will be retrieved to within 1-2% accuracy using a ‘differential’ method, requiring two spectral points for each species - one to sample the spectral line and the other nearby to sample the baseline.An estimation of retrieval errors for the ACCURATE mission reveals that errors in spectroscopic line parameters dominate all other error sources. Poor knowledge of the spectroscopy introduces systematic errors into the retrieved greenhouse gas profiles. Using a simple approach, it was shown that the best line parameters currently available are too large to allow retrievals of greenhouse gases to within the stated ACCURATE mission goals of 1% accuracy for CO₂ and 2% for all other species. Therefore, spectroscopic line parameters for targeted lines need to be improved before the ACCURATE mission can be launched. Requirements have been formulated in this direction, and laboratory experiments outlined that could meet these requirements.     

Heralding two-photon and four-photon path entanglement on a chip

Generating quantum entanglement is not only an important scientific endeavor, but will be essential to realizing quantum-enhanced technologies, in particular, quantum-enhanced measurements with precision beyond classical limits. We investigate the heralded generation of multiphoton entanglement for quantum metrology using a reconfigurable integrated waveguide device in which projective measurement of auxiliary photons heralds the generation of path-entangled states. We use four and six-photon inputs, to analyze the heralding process of two- and four-photon NOON states-a superposition of N photons in two paths, capable of enabling phase supersensitive measurements at the Heisenberg limit. Realistic devices will include imperfections; as part of the heralded state preparation, we demonstrate phase superresolution within our chip with a state that is more robust to photon loss.     

Increase of both order and disorder in the first hydration shell with increasing solute polarity

Monte?Carlo simulations of a small model solute in an aqueous solution are used to examine the effects of solute polarity on hydration structure. A judicious definition of the orientational order parameter leads to reinterpretation of the conventional picture of hydration. As the solute varies from hydrophobic to hydrophilic the ordered first shell water simultaneously fractionates into a more highly ordered and a more disordered component. The hydrogen-bond network rearranges such that the more ordered component relaxes to configurations of optimal intermolecular angles, the other fraction being released from the network.     

The prospects of sympathetic cooling of NH molecules with Li atoms

We calculate the quartet potential energy surface for Li+NH and use it to calculate elastic and spin-relaxation cross sections for collisions in magnetically trappable spin-stretched states. The potential is strongly anisotropic but spin-relaxation collisions are still suppressed by centrifugal barriers when both species are in spin-stretched states. In the ultracold regime, both the elastic and inelastic cross sections fluctuate dramatically as the potential is varied because of Feshbach resonances. The potential-dependence is considerably reduced at higher energies. The major effect of using an unconverged basis set in the scattering calculations is to shift the resonances without changing their general behaviour. We have calculated the ratio of elastic and spin-relaxation cross sections, as a function of collision energy and magnetic field, for a variety of potential energy surfaces. Most of the surfaces produce ratios that are favorable for sympathetic cooling, at temperatures below about 20 mK.     

Numerical simulation of partially coherent broadband optical imaging using the finite-difference time-domain method

Rigorous numerical modeling of optical systems has attracted interest in diverse research areas ranging from biophotonics to photolithography. We report the full-vector electromagnetic numerical simulation of a broadband optical imaging system with partially coherent and unpolarized illumination. The scattering of light from the sample is calculated using the finite-difference time-domain (FDTD) numerical method. Geometrical optics principles are applied to the scattered light to obtain the intensity distribution at the image plane. Multilayered object spaces are also supported by our algorithm. For the first time, numerical FDTD calculations are directly compared to and shown to agree well with broadband experimental microscopy results.     

Measurement of the spatial backscattering impulse-response at short length scales with polarized enhanced backscattering

In this Letter, we describe an easy to implement technique to measure the spatial backscattering impulse-response at length scales shorter than a transport mean free path with resolution of better than 10 μm using the enhanced backscattering phenomenon. This technique enables spectroscopic measurements throughout the visible range and sensitivity to all polarization channels. Through a combination of Monte Carlo simulations and experimental measurements of latex microspheres, we explore the various sensitivities of our technique to both intrinsic sample properties and extrinsic instrumental properties. We conclude by demonstrating the extraordinary sensitivity of our technique to the shape of the scattering phase function, including higher order shape parameters than the anisotropy factor (or first moment).