The ability of the Gaussian-2, Gaussian-3, Complete Basis Set–QB3, and Complete Basis Set–APNO model chemistries to model the geometries of small water clusters

The Gaussian-2, Gaussian-3, Complete Basis Set-QB3, and Complete Basis Set-APNO methods have been used to calculate geometries of neutral clusters of water, (H2O)n, where n = 2–6. The structures are in excellent agreement with those determined from experiment and those predicted from previous high-level calculations. These methods also provide excellent thermochemical predictions for water clusters, and thus can be used with confidence in evaluating the structures and thermochemistry of water clusters.

Do Hydroxyl Radical−Water Clusters, OH(H2O)n, n = 1−5, Exist in the Atmosphere?

It has been speculated that the presence of OH(H2O)n clusters in the troposphere could have significant effects on the solar absorption balance and the reactivity of the hydroxyl radical. We have used the G3 and G3B3 model chemistries to model the structures and predict the frequencies of hydroxyl radical/water clusters containing one to five water molecules. The reaction between hydroxyl radical clusters and methane was examined as a function of water cluster size to gain an understanding of how cluster size affects the hydroxyl radical reactivity.

Prediction of Accurate Anharmonic Experimental Vibrational Frequencies for Water Clusters, (H2O)n, n = 2−5

Accurate anharmonic experimental vibrational frequencies for water clusters consisting of 2−5 water molecules have been predicted on the basis of comparing different methods with MP2/aug-cc-pVTZ calculated and experimental anharmonic frequencies. The combination of using HF/6-31G* scaled frequencies for intramolecular modes and anharmonic frequencies for intermolecular modes gives excellent agreement with experiment for the water dimer and trimer and are as good as the expensive anharmonic MP2 calculations. The water trimer, the cyclic Ci and S4 tetramers, and the cyclic pentamer all have unique peaks in the infrared spectrum between 500 and 800 cm-1 and between 3400 and 3700 cm-1. Under the right experimental conditions these different clusters can be uniquely identified using high-resolution IR spectroscopy.

Ortho Effect in the Bergman Cyclization: Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals

We present a detailed theoretical study of geometries, electronic structure, and energies of transition states and intermediates completing the full Bergman cycloaromatization pathway of ortho-substituted enediynes with a focus on polar and steric contributions to the kinetics and thermodynamics of hydrogen abstraction. This study provides a rare unambiguous example of remote substitution that affects reactivity of a neutral reactive intermediate through an σ framework.

Experimental and Theoretical Study of the OH Vibrational Spectra and Overtone Chemistry of Gas-Phase Vinylacetic Acid

In this study we present the gas-phase vibrational spectrum of vinylacetic acid with a focus on the ν = 1−5 vibrational states of the OH stretching transitions. Cross sections for ν = 1, 2, 4 and 5 of the OH stretching vibrational transitions are derived on the basis of the vapor pressure data obtained for vinylacetic acid. Ab initio calculations are used to assist in the band assignments of the experimental spectra, and to determine the threshold for the decarboxylation of vinylacetic acid. When compared to the theoretical energy barrier to decarboxylation, it is found that the νOH = 4 transition with thermal excitation of low frequency modes or rotational motion and νOH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation.

Comparison of Model Chemistry and Density Functional Theory Thermochemical Predictions with Experiment for Formation of Ionic Clusters of the Ammonium Cation Complexed with Water and Ammonia; Atmospheric Implications

The G2, G3, CBS-QB3, and CBS-APNO model chemistry methods and the B3LYP, B3P86, mPW1PW, and PBE1PBE density functional theory (DFT) methods have been used to calculate ΔH° and ΔG° values for ionic clusters of the ammonium ion complexed with water and ammonia. Results for the clusters NH4+(NH3)n and NH4+(H2O)n, where n = 1−4, are reported in this paper and compared against experimental values. Agreement with the experimental values for ΔH° and ΔG° for formation of NH4+(NH3)n clusters is excellent. Comparison between experiment and theory for formation of the NH4+(H2O)n clusters is quite good considering the uncertainty in the experimental values. The four DFT methods yield excellent agreement with experiment and the model chemistry methods when the aug-cc-pVTZ basis set is used for energetic calculations and the 6-31G* basis set is used for geometries and frequencies. On the basis of these results, we predict that all ions in the lower troposphere will be saturated with at least one complete first hydration shell of water molecules.

Fluorescent Chrysotile From Sterling Hill, New Jersey

Minerals of the serpentine group, notably chrysotile and to a lesser extent lizardite, are widely present at both Franklin and Sterling Hill. They are late-stage hydrous magnesium silicate minerals that formed by hydrothermal alteration of earlier species, among them willemite and tephroite, and are also common components of hydrothermal veins cutting the ore bodies and the enclosing marble (Dunn, 1995). Although long recognized in the area (Fowler, 1825), local serpentine was not documented as a fluorescent mineral until 2004, when a brief description of a fluorescent serpentine from Franklin appeared in The Picking Table (Cianciulli, 2004). In the present paper, we describe additional examples of fluorescent serpentine, most from Sterling Hill.

Femoroacetabular cam-type impingement: diagnostic sensitivity and specificity of radiographic views compared to radial MRI

To retrospectively assess the diagnostic sensitivity of 45° Dunn view and cross-table lateral radiographs for the assessment of cam deformity by comparison with radial MRI.

Aleatory Sovereignty and the Rule of Sensitive Spaces

Addressing life in borders and refugee camps requires understanding the way these spaces are ruled, the kinds of problems rule poses for the people who live there, and the abilities of inhabitants to remake their own lives. Recent literature on such spaces has been influenced by Agamben's notion of sovereignty, which reduces these spaces and their residents to abstractions. We propose an alternate framework focused on what we call aleatory sovereignty, or rule by chance. This allows us to see camps and borders not only as the outcomes of humanitarian projects but also of anxieties about governance and rule; to see their inhabitants not only as abject recipients of aid, but also as individuals who make decisions and choices in complex conditions; and to show that while the outcome of projects within such spaces is often unpredictable, the assumptions that undergird such projects create regular cycles of implementation and failure.

Comparison of six radiographic projections to assess femoral head/neck asphericity

Early radiographic detection of femoroacetabular impingement might prevent initiation and progression of osteoarthritis. The structural abnormality in femoral-induced femoroacetabular impingement (cam type) is frequently asphericity at the anterosuperior head/neck contour. To determine which of six radiographic projections (anteroposterior, Dunn, Dunn/45 degrees flexion, cross-table/15 degrees internal rotation, cross-table/neutral rotation, and cross-table/15 degrees external rotation) best identifies femoral head/neck asphericity, we studied 21 desiccated femurs; 11 with an aspherical femoral head/neck contour and 10 with a spherical femoral head/neck contour. To radiographically quantify femoral head asphericity, we measured the angle where the femoral head/neck leaves sphericity (angle alpha). The aspherical femoral head/neck contours had a greater maximum angle alpha (70 degrees ) compared with the spherical head/neck contours (50 degrees ). The angle alpha varied depending on the radiographic projection: it was greatest in the Dunn view with 45 degrees hip flexion (71 degrees +/- 10 degrees ) and least in the cross-table view in 15 degrees external rotation (51 degrees +/- 7 degrees ). Diagnosis of a pathologic femoral head/neck contour depends on the radiologic projection. The Dunn view in 45 degrees or 90 degrees flexion or a cross-table projection in internal rotation best show femoral head/neck asphericity, whereas anteroposterior or externally rotated cross-table views are likely to miss asphericity. Level of Evidence: Prognostic study, level II-1 (retrospective study).

Non-invasive neurally adjusted ventilatory assist in rabbits with acute lung injury

OBJECTIVE: Neurally adjusted ventilatory assist uses the electrical activity of the diaphragm (EAdi)-a pneumatically-independent signal-to control the timing and pressure of the ventilation delivered, and should not be affected by leaks. The aim of this study was to evaluate whether NAVA can deliver assist in synchrony and proportionally to EAdi after extubation, with a leaky non-invasive interface. DESIGN AND SETTING: Prospective, controlled experimental study in an animal laboratory. ANIMALS: Ten rabbits, anesthetized, mechanically ventilated. INTERVENTIONS: Following lung injury, the following was performed in sequential order: (1) NAVA delivered via oral endotracheal tube with PEEP; (2) same as (1) without PEEP; (3) non-invasive NAVA at unchanged NAVA level and no PEEP via a single nasal prong; (4) no assist; (5) non-invasive NAVA at progressively increasing NAVA levels. MEASUREMENTS AND RESULTS: EAdi, esophageal pressure, blood gases and hemodynamics were measured during each condition. For the same NAVA level, the mean delivered pressure above PEEP increased from 3.9[Symbol: see text]+/-[Symbol: see text]1.4[Symbol: see text]cmH(2)O (intubated) to 7.5[Symbol: see text]+/-[Symbol: see text]3.8[Symbol: see text]cmH(2)O (non-invasive) (p[Symbol: see text]<[Symbol: see text]0.05) because of increased EAdi. No changes were observed in PaO(2) and PaCO(2). Increasing the NAVA level fourfold during non-invasive NAVA restored EAdi and esophageal pressure swings to pre-extubation levels. Triggering (106[Symbol: see text]+/-[Symbol: see text]20[Symbol: see text]ms) and cycling-off delays (40[Symbol: see text]+/-[Symbol: see text]21[Symbol: see text]ms) during intubation were minimal and not worsened by the leak (95[Symbol: see text]+/-[Symbol: see text]13[Symbol: see text]ms and 33[Symbol: see text]+/-[Symbol: see text]9[Symbol: see text]ms, respectively). CONCLUSION: NAVA can be effective in delivering non-invasive ventilation even when the interface with the patient is excessively leaky, and can unload the respiratory muscles while maintaining synchrony with the subject's demand.