2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

Search for color transparency in A(e,e'p) at high momentum transfer

Rates for A(e, e'p) on the nuclei ^2H, C, Fe, and Au have been measured at momentum transfers Q^2 = 1, 3, 5, and 6.8 (GeV fc)^2 . We extract the nuclear transparency T, a measure of the importance of final state interactions (FSI) between the outgoing proton and the recoil nucleus. Some calculations based on perturbative QCD predict an increase in T with momentum transfer, a phenomenon known as Color Transparency. No statistically significant rise is seen in the present experiment.

Variable-angle electron spectroscopic studies of various polyatomic molecular systems

The complementary techniques of low-energy, variable-angle electron-impact spectroscopy and ultraviolet variable-angle photoelectron spectroscopy have been used to study the electronic spectroscopy and structure of several series of molecules. Electron-impact studies were performed at incident beam energies between 25 eV and 100 eV and at scattering angles ranging from 0° to 90°. The energy-loss regions from 0 eV to greater than 15 eV were studied. Photoelectron spectroscopic studies were conducted using a HeI radiation source and spectra were measured at scattering angles from 45° to 90°. The molecules studied were chosen because of their spectroscopic, chemical, and structural interest. The operation of a new electron-impact spectrometer with multiple-mode target source capability is described. This spectrometer has been used to investigate the spin-forbidden transitions in a number of molecular systems.

The electron-impact spectroscopy of the six chloro-substituted ethylenes has been studied over the energy-loss region from 0-15 eV. Spin-forbidden excitations corresponding to the π → π*, N → T transition have been observed at excitation energies ranging from 4.13 eV in vinyl chloride to 3.54 eV in tetrachloroethylene. Symmetry-forbidden transitions of the type π → np have been oberved in trans-dichloroethyene and tetrachlor oethylene. In addition, transitions to many states lying above the first ionization potential were observed for the first time. Many of these bands have been assigned to Rydberg series converging to higher ionization potentials. The trends observed in the measured transition energies for the π → π*, N → T, and N → V as well as the π → 3s excitation are discussed and compared to those observed in the methyl- and fluoro- substituted ethylenes.

The electron energy-loss spectra of the group VIb transition metal hexacarbonyls have been studied in the 0 eV to 15 eV region. The differential cross sections were obtained for several features in the 3-7 eV energy-loss region. The symmetry-forbidden nature of the ¹A_1g → ¹A_1g, 2t_2g(π) → 3t_2g(π*) transition in these compounds was confirmed by the high-energy, low-angle behavior of their relative intensities. Several low lying transitions have been assigned to ligand field transitions on the basis of the energy and angular behavior of the differential cross sections for these transitions. No transitions which could clearly be assigned to singlet → triplet excitations involving metal orbitals were located. A number of states lying above the first ionization potential have been observed for the first time. A number of features in the 6-14 eV energy-loss region of the spectra of these compounds correspond quite well to those observed in free CO.

A number of exploratory studies have been performed. The π → π*, N → T, singlet → triplet excitation has been located in vinyl bromide at 4.05 eV. We have also observed this transition at approximately 3.8 eV in a cis-/trans- mixture of the 1,2-dibromoethylenes. The low-angle spectrum of iron pentacarbonyl was measured over the energy-loss region extending from 2-12 eV. A number of transitions of 8 eV or greater excitation energy were observed for the first time. Cyclopropane was also studied at both high and low angles but no clear evidence for any spin- forbidden transitions was found. The electron-impact spectrum of the methyl radical resulting from the pyrolysis of tetramethyl tin was obtained at 100 eV incident energy and at 0° scattering angle. Transitions observed at 5.70 eV and 8.30 eV agree well with the previous optical results. In addition, a number of bands were observed in the 8-14 eV region which are most likely due to Rydberg transitions converging to the higher ionization potentials of this molecule. This is the first reported electron-impact spectrum of a polyatomic free radical.

Variable-angle photoelectron spectroscopic studies were performed on a series of three-membered-ring heterocyclic compounds. These compounds are of great interest due to their highly unusual structure. Photoelectron angular distributions using HeI radiation have been measured for the first time for ethylene oxide and ethyleneimine. The measured anisotropy parameters, β, along with those measured for cyclopropane were used to confirm the orbital correlations and photoelectron band assignments. No high values of β similar to those expected for alkene π orbitals were observed for the Walsh or Forster-Coulson-Moffit type orbitals.

Did galaxies reionize the universe?

The epoch of reionization remains one of the last uncharted eras of cosmic history, yet this time is of crucial importance, encompassing the formation of both the first galaxies and the first metals in the universe. In this thesis, I present four related projects that both characterize the abundance and properties of these first galaxies and uses follow-up observations of these galaxies to achieve one of the first observations of the neutral fraction of the intergalactic medium during the heart of the reionization era.

First, we present the results of a spectroscopic survey using the Keck telescopes targeting 6.3 < z < 8.8 star-forming galaxies. We secured observations of 19 candidates, initially selected by applying the Lyman break technique to infrared imaging data from the Wide Field Camera 3 (WFC3) onboard the Hubble Space Telescope (HST). This survey builds upon earlier work from Stark et al. (2010, 2011), which showed that star-forming galaxies at 3 < z < 6, when the universe was highly ionized, displayed a significant increase in strong Lyman alpha emission with redshift. Our work uses the LRIS and NIRSPEC instruments to search for Lyman alpha emission in candidates at a greater redshift in the observed near-infrared, in order to discern if this evolution continues, or is quenched by an increase in the neutral fraction of the intergalactic medium. Our spectroscopic observations typically reach a 5-sigma limiting sensitivity of < 50 AA. Despite expecting to detect Lyman alpha at 5-sigma in 7-8 galaxies based on our Monte Carlo simulations, we only achieve secure detections in two of 19 sources. Combining these results with a similar sample of 7 galaxies from Fontana et al. (2010), we determine that these few detections would only occur in < 1% of simulations if the intrinsic distribution was the same as that at z ~ 6. We consider other explanations for this decline, but find the most convincing explanation to be an increase in the neutral fraction of the intergalactic medium. Using theoretical models, we infer a neutral fraction of X_HI ~ 0.44 at z = 7.

Second, we characterize the abundance of star-forming galaxies at z > 6.5 again using WFC3 onboard the HST. This project conducted a detailed search for candidates both in the Hubble Ultra Deep Field as well as a number of additional wider Hubble Space Telescope surveys to construct luminosity functions at both z ~ 7 and 8, reaching 0.65 and 0.25 mag fainter than any previous surveys, respectively. With this increased depth, we achieve some of the most robust constraints on the Schechter function faint end slopes at these redshifts, finding very steep values of alpha_{z~7} = -1.87 +/- 0.18 and alpha_{z~8} = -1.94 +/- 0.23. We discuss these results in the context of cosmic reionization, and show that given reasonable assumptions about the ionizing spectra and escape fraction of ionizing photons, only half the photons needed to maintain reionization are provided by currently observable galaxies at z ~ 7-8. We show that an extension of the luminosity function down to M_{UV} = -13.0, coupled with a low level of star-formation out to higher redshift, can fit all available constraints on the ionization history of the universe.

Third, we investigate the strength of nebular emission in 3 < z < 5 star-forming galaxies. We begin by using the Infrared Array Camera (IRAC) onboard the Spitzer Space Telescope to investigate the strength of H alpha emission in a sample of 3.8 < z < 5.0 spectroscopically confirmed galaxies. We then conduct near-infrared observations of star-forming galaxies at 3 < z < 3.8 to investigate the strength of the [OIII] 4959/5007 and H beta emission lines from the ground using MOSFIRE. In both cases, we uncover near-ubiquitous strong nebular emission, and find excellent agreement between the fluxes derived using the separate methods. For a subset of 9 objects in our MOSFIRE sample that have secure Spitzer IRAC detections, we compare the emission line flux derived from the excess in the K_s band photometry to that derived from direct spectroscopy and find 7 to agree within a factor of 1.6, with only one catastrophic outlier. Finally, for a different subset for which we also have DEIMOS rest-UV spectroscopy, we compare the relative velocities of Lyman alpha and the rest-optical nebular lines which should trace the cites of star-formation. We find a median velocity offset of only v_{Ly alpha} = 149 km/s, significantly less than the 400 km/s observed for star-forming galaxies with weaker Lyman alpha emission at z = 2-3 (Steidel et al. 2010), and show that this decrease can be explained by a decrease in the neutral hydrogen column density covering the galaxy. We discuss how this will imply a lower neutral fraction for a given observed extinction of Lyman alpha when its visibility is used to probe the ionization state of the intergalactic medium.

Finally, we utilize the recent CANDELS wide-field, infra-red photometry over the GOODS-N and S fields to re-analyze the use of Lyman alpha emission to evaluate the neutrality of the intergalactic medium. With this new data, we derive accurate ultraviolet spectral slopes for a sample of 468 3 < z < 6 star-forming galaxies, already observed in the rest-UV with the Keck spectroscopic survey (Stark et al. 2010). We use a Bayesian fitting method which accurately accounts for contamination and obscuration by skylines to derive a relationship between the UV-slope of a galaxy and its intrinsic Lyman alpha equivalent width probability distribution. We then apply this data to spectroscopic surveys during the reionization era, including our own, to accurately interpret the drop in observed Lyman alpha emission. From our most recent such MOSFIRE survey, we also present evidence for the most distant galaxy confirmed through emission line spectroscopy at z = 7.62, as well as a first detection of the CIII]1907/1909 doublet at z > 7.

We conclude the thesis by exploring future prospects and summarizing the results of Robertson et al. (2013). This work synthesizes many of the measurements in this thesis, along with external constraints, to create a model of reionization that fits nearly all available constraints.

Properties of α-monoclinic selenium

The growth of bulky and platelet shaped α-monoclinic crystals is discussed. A simple method is devised for identifying and orienting them.

The density, previously in disagreement with the value calculated from x-ray studies, is carefully redetermined, and found to be in good agreement with the latter.

The relative dielectric constant is determined, an effort being made to eliminate errors inherent in previous measurements, which have not been in agreement. A two parameter model is derived which explains the anisotropy in the relative dielectric constant of orthorhombic sulfur, which is also composed of 8-atom puckered ring molecules. The model works less well for α-monoclinic selenium. The relative dielectric constant anisotropy is quite noticeable, being 6.06 along the crystal b axis, and 8.52-8.93 normal to the axis.

Thin crystal platelets of α-monoclinic selenium (less than 1µ thick) are used to extend optical transmission measurements up to 4.5eV. Previously the measurements extended up to 2.1 eV, limited by the thickness of the available crystals. The absorption edge is at 2.20 eV, with changes in slope of the absorption coefficient occurring at 2.85 eV and 3.8 eV. Measurement of transmission through solutions of selenium in CS_2 and trichlorethylene yield an absorption edge of 2.75 eV. There is evidence the selenium exists in solution partly as Se_8 rings, the building block of monoclinic selenium. Transmission is measured at low temperatures (80°K and 10°K) using the platelets. The absorption edge is at 2.38 eV and 2.39 eV, respectively, for the two temperatures. Measurements at low temperatures with polarized and unpolarized light reveal interesting absorption anisotropy near 2.65 eV.

A study of the ^9 Be nucleus

The reaction ⁷Li(³He, p)⁹Be has been used to measure excitations and intrinsic widths of levels in ⁹Be below the ⁷Li + d threshold. Previously unreported levels have been found at excitations of (13.78 ± .03) MeV and (16.671 ± .008) MeV with widths of (590 ± 60) keV and (41 ± 4) keV respectively. Two overlapping levels have been found at (11.81 ± .02) MeV and (11.29 ± .03) MeV with widths of (400 ± 30) keV and (620 ± 70) keV respectively. Branching ratios from ⁹Be levels populated in this reaction to the ground and first excited states of ⁸Be have been measured by observing the associated protons in coincidence with the decay neutrons. Branching ratios were found to be:

Excitation in ⁹Be .... Branching Ratio.......... Final Nucleus.........

(MeV) .......................... (percent) .....................................

.. 2.43 ........................... 7.5 ± 1.5 .............. ⁸Be(g.s.)

.. 3.03 ........................... 87 ± 13......................................

.. 4.65 ........................... 13 ± 4.......................................

.. 6.76 .............................. ≤ 2 ......................................

.. 11.29 ...............................≤ 2 ......................................

.. 11.81 ...............................≤ 3 ......................................

.. 6.76 ........................... .41 ≤ B.R. ≤ .69 ....... ⁸Be(2⁺)

.. 11.29 ........................... 14 ± 4 .......................................

.. 11.81 ........................... 12 ± 4 .......................................

Corresponding reduced widths for neutron emission are calculated and a comparison of the results with the expectations of current nuclear models is made. In particular the measured branching ratio to ⁸Be(g.s.) from ⁹Be(2.43 MeV) corresponds to an f-wave reduced with θ²_f = 2.1 x 10^-2, in units of ħ²/mR², with R = 4.35 fm. A comparison of this value with that predicted by a Nilsson model calculation, in which ⁹Be is taken to be a deformed nucleus, is discussed. The measured value for θ²_f is found to be consistent with that expected on the basis of measured E2-transition rates between rotational levels in ⁹Be.