646 research outputs found
Administrative Performance of “No-Fault” Compensation for Medical Injury
No-fault is the leading alternative to traditional liability systems for resolving medically caused injuries, and policy interest in such reform reflects numerous concerns with the traditional tort system as it operates in the medical field through malpractice insurance. The administrative experience of the Florida and Virginia no-fault programs is examined
The R\"uchardt experiment revisited: using simple theory, accurate measurement and python based data analysis
This project uses the R\"uchardt experiment to determine the ratio of
specific heats and hence the number of degrees of freedom of different
gases by measuring the frequency of damped simple harmonic motion where the gas
provides the Hooke's law like spring of a cylinder-piston system. This project
links mechanics, electromagnetism, thermodynamics, statistical mechanics and
quantum mechanics making it an excellent synoptic experiment for a mid year
undergraduate student. We present simple derivations of the main relationships
that govern the experiment, a detailed data analysis of the physics of the
apparatus and of the experimental data. We find , , ,
at room temperature and atmospheric
pressure. The results for CO requires a statistical analysis of its
vibrational modes. These results show that the expected results can be measured
using fairly simple apparatus, coupled with careful analysis of large data
sets.Comment: 24 pages, 8 figure
Solid Solid Phase Transitions and tert-Butyl and Methyl Group Rotation in an Organic Solid: X-ray Diffractometry, Differential Scanning Calorimetry, and Solid-State H-1 Nuclear Spin Relaxation
Using solid state 1H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments, we have investigated the effects of several solid-solid phase transitions on t-butyl group and methyl group rotation in solid 1,3,5-tri-t-butylbenzene. The goal is to relate the dynamics of the t-butyl groups and their constituent methyl groups to properties of the solid determined using single-crystal X-ray diffraction and differential scanning calorimetry (DSC). On cooling, the DSC experiments see a first-order, solid-solid phase transition at either 268 K or 155 K (but not both) depending on thermal history. The 155 K transition (on cooling) is identified by single-crystal X-ray diffraction to be one from a monoclinic phase (above 155 K) where the t-butyl groups are disordered (that is, with a rotational six-fold intermolecular potential dominating) to a triclinic phase (below 155 K) where the t-butyl groups are ordered (that is, with a rotational threefold intermolecular potential dominating). This transition shows very different DSC scans when both a 5 mg polycrystalline sample and a 19 mg powder sample are used. The 1H spin-lattice relaxation experiments with a much larger 0.7 g sample are very complicated and, depending on thermal history, can show hysteresis effects over many hours and over very large temperature ranges. In the high-temperature monoclinic phase, the t-butyl groups rotate with NMR activation energies (closely related to rotational barriers) in the 17-23 kJ mol-1 range and the constituent methyl groups rotate with NMR activation energies in the 7-12 kJ mol-1 range. In the lowtemperature triclinic phase, the rotations of the t-butyl groups and their methyl group in the aromatic plane are quenched (on the NMR time scale). The two out-of-plane methyl groups in the t-butyl groups are rotating with activation energies in the 5-11 kJ mol-1 range
Solid Solid Phase Transitions and tert-Butyl and Methyl Group Rotation in an Organic Solid: X-ray Diffractometry, Differential Scanning Calorimetry, and Solid-State H-1 Nuclear Spin Relaxation
Using solid state 1H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments, we have investigated the effects of several solid-solid phase transitions on t-butyl group and methyl group rotation in solid 1,3,5-tri-t-butylbenzene. The goal is to relate the dynamics of the t-butyl groups and their constituent methyl groups to properties of the solid determined using single-crystal X-ray diffraction and differential scanning calorimetry (DSC). On cooling, the DSC experiments see a first-order, solid-solid phase transition at either 268 K or 155 K (but not both) depending on thermal history. The 155 K transition (on cooling) is identified by single-crystal X-ray diffraction to be one from a monoclinic phase (above 155 K) where the t-butyl groups are disordered (that is, with a rotational six-fold intermolecular potential dominating) to a triclinic phase (below 155 K) where the t-butyl groups are ordered (that is, with a rotational threefold intermolecular potential dominating). This transition shows very different DSC scans when both a 5 mg polycrystalline sample and a 19 mg powder sample are used. The 1H spin-lattice relaxation experiments with a much larger 0.7 g sample are very complicated and, depending on thermal history, can show hysteresis effects over many hours and over very large temperature ranges. In the high-temperature monoclinic phase, the t-butyl groups rotate with NMR activation energies (closely related to rotational barriers) in the 17-23 kJ mol-1 range and the constituent methyl groups rotate with NMR activation energies in the 7-12 kJ mol-1 range. In the lowtemperature triclinic phase, the rotations of the t-butyl groups and their methyl group in the aromatic plane are quenched (on the NMR time scale). The two out-of-plane methyl groups in the t-butyl groups are rotating with activation energies in the 5-11 kJ mol-1 range
H2, HD, and D2 in the small cage of structure II clathrate hydrate: vibrational frequency shifts from fully coupled quantum six-dimensional calculations of the vibration-translation-rotation eigenstates
We report the first fully coupled quantum six-dimensional (6D) bound-state calculations of the vibration-translation-rotation eigenstates of a flexible H2, HD, and D2 molecule confined inside the small cage of the structure II clathrate hydrate embedded in larger hydrate domains with up to 76 H2O molecules, treated as rigid. Our calculations use a pairwise-additive 6D intermolecular potential energy surface for H2 in the hydrate domain, based on an ab initio 6D H2–H2O pair potential for flexible H2 and rigid H2O. They extend to the first excited (v = 1) vibrational state of H2, along with two isotopologues, providing a direct computation of vibrational frequency shifts. We show that obtaining a converged v = 1 vibrational state of the caged molecule does not require converging the very large number of intermolecular translation-rotation states belonging to the v = 0 manifold up to the energy of the intramolecular stretch fundamental (≈4100 cm−1 for H2). Only a relatively modest-size basis for the intermolecular degrees of freedom is needed to accurately describe the vibrational averaging over the delocalized wave function of the quantum ground state of the system. For the caged H2, our computed fundamental translational excitations, rotational j = 0 → 1 transitions, and frequency shifts of the stretch fundamental are in excellent agreement with recent quantum 5D (rigid H2) results [A. Powers et al., J. Chem. Phys. 148, 144304 (2018)]. Our computed frequency shift of −43 cm−1 for H2 is only 14% away from the experimental value at 20 K
Fitting of dust spectra with genetic algorithms - I. Perspectives & Limitations
Aims: We present an automatised fitting procedure for the IR range of AGB
star spectra. Furthermore we explore the possibilities and boundaries of this
method. Methods: We combine the radiative transfer code DUSTY with the genetic
algorithm PIKAIA in order to improve an existing spectral fit significantly.
Results: In order to test the routine we carried out a performance test by
feeding an artificially generated input spectrum into the program. Indeed the
routine performed as expected, so, as a more realistic test set-up, we tried to
create model fits for ISO spectra of selected AGB stars. Here we were not only
able to improve existing fits, but also to show that a slightly altered dust
composition may give a better fit for some objects. Conclusion: The use of a
genetic algorithm in order to automatise the process of fitting stellar spectra
seems to be very promising. We were able to improve existing fits and further
offer a quantitative method to compare different models with each other.
Nevertheless this method still needs to be studied and tested in more detail.Comment: 9 pages, 5 figures, accepted for publication in Astronomy and
Astrophysic
Concerted thermal-plus-electronic nonlocal desorption of chlorobenzene from Si(111)-7 × 7 in the STM
The rate of desorption of chemisorbed chlorobenzene molecules from the Si(111)-7 × 7 surface, induced by nonlocal charge injection from an STM tip, depends on the surface temperature. Between 260 and 313 K, we find an Arrhenius thermal activation energy of 450 ± 170 meV, consistent with the binding energy of physisorbed chlorobenzene on the same surface. Injected electrons excite the chlorobenzene molecule from the chemisorption state to an intermediate physisorption state, followed by thermal desorption. We find a second thermal activation energy of 21 ± 4 meV in the lower temperature region between 77 and 260 K, assigned to surface phonon excitation
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