Experimental characterization of SiCH+via single-photon ionization of gas-phase SiCH.

SiCH and its cation have consistently emerged as predicted species in models of silicon chemistry within the interstellar medium, although they remain unobserved in space. Hindered by their intrinsic instability, no spectroscopic insights have been gleaned concerning the SiCH+ cation. In this study, we present experimental measurements on the SiCH+ cation through single-photon ionization spectroscopy of the SiCH radical within the 8.0-11.0 eV range. Gas-phase SiCH radicals were generated through chemical reactions involving CHx (x = 0-3) and SiHy (y = 0-3) within a microwave discharge flow-tube reactor. Employing a double imaging photoelectron/photoion coincidence spectrometer on the DESIRS beamline at the SOLEIL synchrotron, we recorded mass-selected ion yield and photoelectron spectra. From the analysis of the photoelectron spectrum supported by ab initio calculations and Franck-Condon simulations, the adiabatic ionization energies for the transitions from the X2Π ground electronic state of SiCH toward the X+3Σ- and A+3Π electronic states of SiCH+ have been derived [8.935(6) and 10.664(6) eV, respectively, without spin-orbit correction]. The contribution from the less stable isomer HSiC has been explored in our analysis and ruled out in our experiments.

Single-photon ionization of SiC in the gas phase: experimental and ab initio characterization of SiC.

We report the first experimental observation of single-photon ionization transitions of the SiC radical between 8.0 and 11.0 eV performed on the DESIRS beamline at the SOLEIL synchrotron facility. The SiC radical, very difficult to synthesize in the gas phase, was produced through chemical reactions between CHx (x = 0-3) and SiHy (y = 0-3) in a continuous microwave discharge flow tube, the CHx and SiHy species being formed by successive hydrogen-atom abstractions induced by fluorine atoms on methane and silane, respectively. Mass-selected ion yield and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The photoelectron spectrum enables the first direct experimental determinations of the X+ 4Σ- ← X 3Π and 1+ 2Π â† X 3Π adiabatic ionization energies of SiC (8.978(10) eV and 10.216(24) eV, respectively). Calculated spectra based on Franck-Condon factors are compared with the experimental spectra. These spectra were obtained by solving the rovibrational Hamiltonian, using the potential energy curves calculated at the multireference single and double configuration interaction level with Davidson correction (MRCI + Q) and the aug-cc-pV5Z basis set. MRCI + Q calculations including the core and core-valence electron correlation were performed using the aug-cc-pCV6Z basis set to predict the spectroscopic properties of the six lowest electronic states of SiC+. Complete basis set extrapolations and relativistic energy corrections were also included in the determination of the energy differences characterizing the photoionization process. Using our experimental and theoretical results, we derived semi-experimental values for the five lowest ionization energies of SiC.

Photoionization of C4H5 Isomers.

Single-photon, photoelectron-photoion coincidence spectroscopy is used to record the mass-selected ion spectra and slow photoelectron spectra of C4H5 radicals produced by the abstraction of hydrogen atoms from three C4H6 precursors by fluorine atoms generated by a microwave discharge. Three different C4H5 isomers are identified, with the relative abundances depending on the nature of the precursor (1-butyne, 1,2-butadiene, and 1,3-butadiene). The results are compared with our previous work using 2-butyne as a precursor [Hrodmarsson, H. R. J. Phys. Chem. A 2019, 123, 1521-1528]. The slow photoelectron spectra provide new information on the three radical isomers that is in good agreement with previous experimental and theoretical results [Lang, M. J. Phys. Chem. A 2015, 119, 3995-4000; Hansen, N. J. Phys. Chem. A 2006, 110, 3670-3678]. The energy scans of the C4H5 photoionization signal are recorded with substantially better resolution and signal-to-noise ratio than those in earlier work, allowing the observation of autoionizing resonances based on excited states of the C4H5 cation. Photoelectron images recorded at several energies are also reported, providing insight into the decay processes of these excited states. Finally, in contrast to the earlier work using 2-butyne as a precursor, where H-atom abstraction was the only observed process, F- and H-atom additions to the present precursors are also observed through the detection of C4H6F, C4H5F, and C4H7.

Quantifying the photoionization cross section of the hydroxyl radical.

The hydroxyl free radical, OH, is one of the most important radicals in atmospheric and interstellar chemistry, and its cation plays a role in the reactions leading to H2O formation. Knowledge of the photoionization efficiency of the OH radical is crucial to properly model the water photochemical cycle of atmospheres and astrophysical objects. Using a gas-phase radical source based on a single H-abstraction reaction combined with a photoelectron/photoion imaging coincidence spectrometer coupled with synchrotron radiation, we recorded the OH+ photoion yield over the 12.6-15 eV energy range, and we set it to an absolute cross section scale using an absolute point measurement performed at 13.8 eV: σOH ion=9.0±2.7 Mb. The resulting cross section values differ by approximately a factor 2 from the recent measurement of Dodson et al. [J. Chem. Phys. 148, 184302 (2018)] performed with a different radical source, which is somewhat greater than the combined uncertainties of the measurements. This finding underlines the need for further investigations of this cross section.

Valence-Shell Photoionization of C4H5: The 2-Butyn-1-yl Radical.

We present new high-resolution data on the photoionization of the 2-butyn-1-yl radical (CH3C≡C-•CH2) formed by H atom abstraction from 2-butyne by F atoms. The spectra were recorded from 7.7 to 11 eV by using double-imaging, photoelectron-photoion coincidence spectroscopy, which allows the unambiguous correlation of photoelectron data and the mass of the species. The photoionization spectrum shows significant resonant autoionizing structure converging to excited states of the C4H5+ cation, similar to what is observed in the closely related propargyl radical (HC≡C-•CH2). The threshold photoelectron spectrum, obtained with a resolution of 17 meV, is also reported. This spectrum is consistent with previous measurements of the first photoionization band but has been extended to higher energy to allow the observation of bands corresponding to excited electronic states of the ion. A refined value of the adiabatic ionization energy is extracted: IE(C4H5) = 7.93 ± 0.01 eV. A determination of the absolute photoionization cross section of the 2-butyn-1-yl radical at 9.7 eV is also reported: σion(C4H5) = 6.1 ± 1.8 Mb.

Experimental and theoretical threshold photoelectron spectra of methylene.

The threshold photoelectron spectrum of methylene (CH2), produced by consecutive H atom abstractions on methane, has been recorded using synchrotron radiation. The experimental spectrum spans the region of the X + 2Π u ← X 3 B 1 ionizing transition. It is modeled starting from ab initio bending potentials and using the bending approach introduced by Coudert et al. [J. Chem. Phys. 148, 054302 (2018)] accounting for the quasilinearity of CH2 and the strong Renner-Teller interaction in CH 2 + . This first calculation yields a theoretical threshold photoelectron spectrum which is in moderate agreement with the experimental one. A more accurate approach treating the three vibrational modes is developed for computing the threshold photoelectron spectrum of triatomic C 2 v molecules. This new treatment is tested modeling the already measured threshold photoelectron spectrum of the X + 2Π u ← X 1 A 1 ionizing transition of the water molecule. The threshold photoelectron spectrum of CH2 computed with the new approach compares more favorably with the experimental spectrum and yields an adiabatic ionization potential of 10.386(6) eV.

Photoelectron angular distributions from rotationally resolved autoionizing states of N2.

The single-photon, photoelectron-photoion coincidence spectrum of N2 has been recorded at high (∼1.5 cm-1) resolution in the region between the N2+ X Σg2+, v+ = 0 and 1 ionization thresholds by using a double-imaging spectrometer and intense vacuum-ultraviolet light from the Synchrotron SOLEIL. This approach provides the relative photoionization cross section, the photoelectron energy distribution, and the photoelectron angular distribution as a function of photon energy. The region of interest contains autoionizing valence states, vibrationally autoionizing Rydberg states converging to vibrationally excited levels of the N2+ X Σg2+ ground state, and electronically autoionizing states converging to the N2+A2Π and B 2Σu+ states. The wavelength resolution is sufficient to resolve rotational structure in the autoionizing states, but the electron energy resolution is insufficient to resolve rotational structure in the photoion spectrum. A simplified approach based on multichannel quantum defect theory is used to predict the photoelectron angular distribution parameters, ß, and the results are in reasonably good agreement with experiment.

Communication: On the first ionization threshold of the C2H radical.

The slow photoelectron spectrum of the ethynyl radical has been recorded for the first time by using the DESIRS beamline of the SOLEIL synchrotron facility. Ethynyl was generated using a microwave discharge flow tube. The observation of the X+Π3←XΣ+2 transition allowed the first direct measurement of the adiabatic ionization threshold of this radical (EI = 11.641(5) eV). The experimental results are supported by ab initio calculations. Our preliminary investigation of the cationic ground state potential energy surfaces predicts a non-negligible Renner-Teller effect which has not been discussed previously.

Synchrotron-based valence shell photoionization of CH radical.

We report the first experimental observations of X(+) (1)Σ(+)←X (2)Π and a(+) (3)Π←X (2)Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne.

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydberg states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. This type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n ≥ 5 manifolds of excited states of larger molecules.

On the adiabatic ionization energy of the propargyl radical.

The photoionization and pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the propargyl radical have been recorded in the vicinity of the origin of the X(+) (1)A1←X(2)B1 photoionizing transition. An internally cold sample of propargyl with a rotational temperature of ~45 K was produced in a supersonic expansion of 1,3-butadiene in helium. Propargyl was generated by excimer laser (ArF, 193 nm) photolysis of 1,3-butadiene in a quartz capillary mounted at the exit of a pulsed valve. The rotational structure of the origin band of the photoelectron spectrum was partially resolved and an improved value of the adiabatic ionization energy of propargyl (E(I)/hc = 70174.5(20) cm(-1)) was determined.

Linear viscoelasticity of an inverse ferrofluid.

A magnetorheological fluid consisting of colloidal silica spheres suspended in an organic ferrofluid is described. Its linear viscoelastic behavior as a function of frequency, magnetic field strength, and silica volume fraction was investigated with a specially designed magnetorheometer. The storage modulus G' is at least an order of magnitude larger than the loss modulus G" at all magnetic field strengths investigated. G' does depend only weakly on frequency, and linearly on volume fraction. A model is presented for the high frequency limit of the storage modulus G'(infinity). In the model our system is treated as a collection of single noninteracting chains of particles. Assuming a dipolar magnetic interaction, theory and experiment show reasonable agreement at high frequencies.

Precise localization of the motor nerve branches to the hamstring muscles: an aid to the conduct of neurolytic procedures.

OBJECTIVE: To identify the precise locations of the motor branches and motor points to the hamstring musculature and define these locations in relation to bony landmarks. DESIGN: Descriptive study of adult cadaver limb dissection. The number, location, and course of the motor branches and motor points to each hamstring muscle from the sciatic nerve were defined relative to bony landmarks. SETTING: Department of anatomy at a university school of medicine. PARTICIPANTS: Anatomic dissection of 30 adult cadaver limbs (17 individuals) was completed. Adult cadavers were selected randomly without regard to gender, age, and race. Exclusion criteria included femoral fracture, surgery, inability to obtain neutral position, and posterior thigh trauma. MAIN OUTCOME MEASURE: A descriptive anatomic study based on linear measures in centimeters from bony landmarks. RESULTS: Two zones located along a line from the ischial tuberosity to the lateral femoral condyle were observed to exist. Zone one, containing the first motor branch to the biceps long head and semitendinosus, is found at approximately 20% (6.9cm +/- 1.8 and 7.1cm +/- 2.2 from the ischial tuberosity, respectively) of femur length along the stated line. Zone two, containing the primary branch to the semimembranosus and the secondary branches to the biceps and semitendinosus, is found at approximately 33% (13.1cm +/- 3.6, 12.6cm +/- 3.9, and 14.3cm +/- 3.9 from the ischial tuberosity, respectively) of femur length. CONCLUSIONS: The drawing of one surface line, when combined with our anthropometric observations, should increase the ease and accuracy with which motor branch blocks to the hamstrings are performed.

Physical medicine and rehabilitation workforce study: the supply of and demand for physiatrists.

OBJECTIVE: Analysis, results, and implications of a supply and demand workforce model for physical medicine and rehabilitation. Explicit issues addressed include: (1) the supply implications of maintaining current (1994-1995) output of physiatrists from residency programs; (2) the implications of continued growth in managed care on the demand for the services of physiatrists; (3) likely future supply and demand conditions; and (4) strategies to adapt to future conditions. DESIGN: A workforce model of the supply and demand for physiatrists was developed. Parameters of the model are estimated using econometric models and by applying the judgments of a consensus panel. The model evaluated several different scenarios regarding managed care growth, competition from other providers and other factors. RESULTS: Based on the analysis, physiatrists will continue to be in excess demand through the year 2000. More aggressive growth in managed care can affect this result. CONCLUSIONS: Based on an overall assessment of supply and demand conditions, and under the assumption that the supply of new entrants each year remains in the range of 1994-1995 levels, demand for physiatrists will continue to exceed supply, on average, through the year 2000. Excess supply has, and will, emerge in selected geographic areas. If the profession is successful in informing the market regarding the advantages of physiatry, the profession can continue to grow without experiencing excess supply, in the aggregate, for the foreseeable future.

Delivery of primary care to the physically challenged.

The specialty of physical medicine and rehabilitation evolved beyond conventional medical views to include consideration of the needs of the physically disabled person's function and quality of life. A care delivery system of medical rehabilitation programs and services then evolved. Recently, the United States' health care system has been recognized as being deficient in meeting the on-going health care needs of the physically disabled after they have completed medical rehabilitation needs. We discuss the history of the health care needs of the physically challenged and we examine current issues of need and delivery of services. We also describe an innovative model program designed to meet those needs.