Experiment in Quantization: Atomic Line Spectra

Laboratory exercises that confront students with decisive ouantum ohenomena nrovide valuable motivation for the kudy of quantum m&hanics. The idea that microscopic matter exists in quantized states can be demonstrated with modern versions of historic experiments: atomic line snectra. blackbodv radiation. and resonance potentials. In this experiment, we present a strikingly simple and visual method for determining the wavelength of spectral lines. This experiment not only shows the inadequacy of classical physics, but also indicates the power of optical measurements.

Exploration of the Potential Energy Surfaces, Prediction of Atmospheric Concentrations, and Prediction of Vibrational Spectra for the HO2···(H2O)n (n = 1−2) Hydrogen Bonded Complexes

The hydroperoxy radical (HO2) plays a critical role in Earth's atmospheric chemistry as a component of many important reactions. The self-reaction of hydroperoxy radicals in the gas phase is strongly affected by the presence of water vapor. In this work, we explore the potential energy surfaces of hydroperoxy radicals hydrogen bonded to one or two water molecules, and predict atmospheric concentrations and vibrational spectra of these complexes. We predict that when the HO2 concentration is on the order of 108molecules·cm-3 at 298 K, that the number of HO2···H2O complexes is on the order of 107molecules·cm-3 and the number of HO2···(H2O)2 complexes is on the order of 106molecules·cm-3. Using the computed abundance of HO2···H2O, we predict that, at 298 K, the bimolecular rate constant for HO2···H2O + HO2 is about 10 times that for HO2 + HO2.

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.

Doubly charged ion mass spectra of alkyl-substituted furans and pyrroles

Doubly charged ion mass spectra of alkyl-substituted furans and pyrroles were obtained using a double-focusing magnetic mass spectrometer operated at 3.2 kV accelerating voltage. Molecular ions were the dominant species found in doubly charged spectra of lower molecular weight heterocydic compounds, whereas the spectra of the higher weight homologues were typified by abundant fragment ions from extensive decomposition. Measured doubly charged ionization and appearance energies ranged from 22.8 to 47.9 eV. Ionization energies were correlated with values calculated using self-consistent field–molecular orbital techniques. A multichannel diabatic curve-crossing model was developed to investigate the fundamental organic ion reactions responsible for development of doubly charged ion mass spectra. Probabilities for Landau–Zener type transitions between reactant and product curves were determined and used in the collision model to predict charge-transfer cross-sections, which compared favorably with experimental cross-sections obtained using time-of-flight techniques.

Sensitivity Gains, Linearity, and Spectral Reproducibility in Nonuniformly Sampled Multidimensional MAS NMR Spectra of High Dynamic Range

Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear C-13-C-13 correlation spectra. We demonstrate on model compounds and on 1-73-(U-C-13,N-15)/74-108-(U-N-15) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7-2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear C-13-C-13 MAS correlation experiments that yield high-quality artifact-free datasets.

A Stellar Census of the Tucana-Horologium Moving Group

We report the selection and spectroscopic confirmation of 129 new late-type (SpT = K3-M6) members of the Tucana-Horologium moving group, a nearby (d similar to 40 pc), young (tau similar to 40 Myr) population of comoving stars. We also report observations for 13 of the 17 known Tuc-Hor members in this spectral type range, and that 62 additional candidates are likely to be unassociated field stars; the confirmation frequency for new candidates is therefore 129/191 = 67%. We have used radial velocities, Ha emission, and Li-6708 absorption to distinguish between contaminants and bona fide members. Our expanded census of Tuc-Hor increases the known population by a factor of similar to 3 in total and by a factor of similar to 8 for members with SpT >= K3, but even so, the K-M dwarf population of Tuc-Hor is still markedly incomplete. Our expanded census allows for a much more detailed study of Tuc-Hor than was previously feasible. The spatial distribution of members appears to trace a two-dimensional sheet, with a broad distribution in X and Y, but a very narrow distribution (+/- 5 pc) in Z. The corresponding velocity distribution is very small, with a scatter of +/- 1.1 km s(-1) about the mean UVW velocity for stars spanning the entire 50 pc extent of Tuc-Hor. We also show that the isochronal age (tau similar to 20-30 Myr) and the lithium depletion boundary age (tau similar to 40 Myr) disagree, following the trend in other pre-main-sequence populations for isochrones to yield systematically younger ages. The H alpha emission line strength follows a trend of increasing equivalent width with later spectral type, as is seen for young clusters. We find that moving group members have been depleted of measurable lithium for spectral types of K7.0-M4.5. None of our targets have significant infrared excesses in the WISE W3 band, yielding an upper limit on warm debris disks of F < 0.7%. Finally, our purely kinematic and color-magnitude selection procedure allows us to test the efficiency and completeness for activity-based selection of young stars. We find that 60% of K-M dwarfs in Tuc-Hor do not have ROSAT counterparts and would have been omitted in X-ray-selected samples. In contrast, GALEX UV-selected samples using a previously suggested criterion for youth achieve completeness of 77% and purity of 78%, and we suggest new SpT-dependent selection criteria that will yield > 95% completeness for tau similar to 40 Myr populations with GALEX data available.