VESPA: The vibrational spectrometer for the European Spallation Source.

VESPA, Vibrational Excitation Spectrometer with Pyrolytic-graphite Analysers, aims to probe molecular excitations via inelastic neutron scattering. It is a thermal high resolution inverted geometry time-of-flight instrument designed to maximise the use of the long pulse of the European Spallation Source. The wavelength frame multiplication technique was applied to provide simultaneously a broad dynamic range (about 0-500 meV) while a system of optical blind choppers allows to trade flux for energy resolution. Thanks to its high flux, VESPA will allow the investigation of dynamical and in situ experiments in physical chemistry. Here we describe the design parameters and the corresponding McStas simulations.

High pressure optical cell for synthesis and in situ Raman spectroscopy of hydrogen clathrate hydrates.

We report the design, realization, and test of a high-pressure optical cell that we have used to measure the Raman spectra of hydrogen clathrate hydrates, synthesized in situ by the application of 200-300 MPa of gas pressure on solid water. The optical apparatus is mounted on a cryogenic system so to allow measurements and sample treatment at any temperature between 300 and 20 K. A capillary pipe is connected to the inside of the cell to allow the gas flow into and out of the cell, and to regulate the internal pressure at any value from 0 to 300 MPa. In the experimental test described in this paper, the cell has been partly filled, at room temperature, with a small amount of water, then frozen at 263 K before injecting hydrogen gas, at pressure of 150 MPa, into the cell. This procedure has permitted to study hydrogen clathrate formation, by measuring Raman spectra as a function of time.

Realization of an ultrastable 578-nm laser for an Yb lattice clock.

In this paper, we describe the development of an ultrastable laser source at 578 nm, realized using frequency sum generation. This source will be used to excite the clock transition (1)S(0) - (3)P(0) in an ytterbium optical lattice clock experiment. Two independent ultrastable lasers have been realized, and the laser frequency noise and stability have been characterized.

Experimental and theoretical analysis of the rotational Raman spectrum of hydrogen molecules in clathrate hydrates.

The Raman spectra of H(2) and HD molecules in simple hydrogen and binary hydrogen-tetrahydrofuran clathrate hydrates have been measured at temperatures as low as 20 K. The rotational bands of trapped molecules in simple and binary hydrates have been analyzed, and the contributions originating from hydrogen molecules in the large cages have been separated from those in the small cages. A theoretical model, consisting in rigid cages enclosing interacting hydrogen molecules, has been exploited to calculate, on the basis of quantum mechanics, the Raman intensity of the rotational transitions for up to two interacting molecules in one cage. A comparison with experiment leads to a clear interpretation of sidebands appearing in the Raman rotational lines. The quantitative agreement between theory and experiment obtained in some cases clarifies the importance of the choice of the interaction potential, and of the proton disorder in the clathrate crystal.

High capacity hydrogen adsorption in Cu(II) tetracarboxylate framework materials: the role of pore size, ligand functionalization, and exposed metal sites.

A series of isostructural metal-organic framework polymers of composition [Cu2(L)(H2O)2] (L= tetracarboxylate ligands), denoted NOTT-nnn, has been synthesized and characterized. Single crystal X-ray structures confirm the complexes to contain binuclear Cu(II) paddlewheel nodes each bridged by four carboxylate centers to give a NbO-type network of 64.82 topology. These complexes are activated by solvent exchange with acetone coupled to heating cycles under vacuum to afford the desolvated porous materials NOTT-100 to NOTT-109. These incorporate a vacant coordination site at each Cu(II) center and have large pore volumes that contribute to the observed high H2 adsorption. Indeed, NOTT-103 at 77 K and 60 bar shows a very high total H2 adsorption of 77.8 mg g(-)- equivalent to 7.78 wt% [wt% = (weight of adsorbed H2)/(weight of host material)] or 7.22 wt% [wt% = 100(weight of adsorbed H2)/(weight of host material + weight of adsorbed H2)]. Neutron powder diffraction studies on NOTT-101 reveal three adsorption sites for this material: at the exposed Cu(II) coordination site, at the pocket formed by three {Cu2} paddle wheels, and at the cusp of three phenyl rings. Systematic virial analysis of the H2 isotherms suggests that the H2 binding energies at these sites are very similar and the differences are smaller than 1.0 kJ mol-1, although the adsorption enthalpies for H2 at the exposed Cu(II) site are significantly affected by pore metrics. Introducing methyl groups or using kinked ligands to create smaller pores can enhance the isosteric heat of adsorption and improve H2 adsorption. However, although increasing the overlap of potential energy fields of pore walls increases the heat of H2 adsorption at low pressure, it may be detrimental to the overall adsorption capacity by reducing the pore volume.

Low temperature Raman spectra of hydrogen in simple and binary clathrate hydrates.

The Raman spectrum of hydrogen clathrate hydrates has been measured, as a function of temperature, down to 20 K. Rotational bands of H(2) and HD, trapped into the small cages of simple (H(2)O-H(2)) and binary (H(2)O-THF-H(2)) hydrates, have been analyzed and the fivefold degeneracy of the molecular J=2 rotational level has been discussed in the light of the available theoretical calculations. The vibrational frequencies of H(2) molecules encapsulated in the large cages of simple hydrates turn out to be well separated from those pertaining to the small cages. Comparison with the equivalent D(2) spectra allowed us to assign the large cavity vibrational frequencies to three couples of Q(1)(1)-Q(1)(0) H(2) vibrational modes. Populations of ortho and para species have been measured as a function of time from rotational spectra and the rate of ortho-para conversion has been estimated for both simple and binary hydrates. We suggest, using the H(2) vibrational spectra, a model to analyze the cage population in simple hydrates.

Comparison of regional anesthesia versus combined regional and general anesthesia for elective carotid endarterectomy: a small exploratory study.

BACKGROUND AND OBJECTIVES: This is a small pilot study to compare hemodynamic stability during carotid endarterectomy performed with either regional anesthesia or combined regional/general anesthesia. METHODS: Twenty-eight patients undergoing elective carotid endarterectomy were randomly assigned to: (1) superficial cervical plexus block (n = 14); or (2) superficial cervical plexus block plus general anesthesia (n = 14). The primary outcome measure was hemodynamic stability as indicated by blood pressure changes. Mean arterial pressure was recorded at different times (T(0), T(1), T(2), T(3)). Surgery duration, carotid cross-clamping time, time to recovery of consciousness, perioperative complications, requirement for antihypertensive or antihypotensive drugs, and lidocaine supplementation were recorded. Patients were asked to grade their intraoperative comfort. RESULTS: In group 1, mean arterial pressure was higher at T(1) and T(2) compared with group 2 (P < .001). Hedges' g effect size was 2.47 (95% confidence interval [CI], 1.48-3.45) at T(1) (very large effect) and 1.36 (95% CI, 0.54-2.18) at T(2) (large effect). Surgery duration was 106 +/- 28 minutes in group 1 versus 91 +/- 16 in group 2 (P = .1026). Carotid cross-clamping time was 45 +/- 14 minutes in group 1 versus 36 +/- 9 in group 2 (P = .0503). Comfort and analgesia were better in group 2 (1.43 +/- 0.65) than in group 1 (2.21 +/- 0.7) (P = .0053). CONCLUSIONS: This pilot study suggests that combined regional/general anesthesia provides greater hemodynamic stability and patient comfort compared with regional anesthesia during carotid endarterectomy. Further studies are warranted before conclusions can be drawn as to the efficacy and safety of the technique.

Microscopic distribution functions, structure, and kinetic energy of liquid and solid neon: quantum Monte Carlo simulations.

We have performed extensive path integral Monte Carlo simulations of liquid and solid neon, in order to derive the kinetic energy as well as the single-particle and pair distribution functions of neon atoms in the condensed phases. From the single-particle distribution function n(r) one can derive the momentum distribution and thus obtain an independent estimate of the kinetic energy. The simulations have been carried out using mostly the semiempirical HFD-C2 pair potential by Aziz et al. [R. A. Aziz, W. J. Meath, and A. R. Allnatt, Chem. Phys. 79, 295 (1983)], but, in a few cases, we have also used the Lennard-Jones potential. The differences between the potentials, as measured by the properties investigated, are not very large, especially when compared with the actual precision of the experimental data. The simulation results have been compared with all the experimental information that is available from neutron scattering. The overall agreement with the experiments is very good.