The structure of the triethylenediamine molecule in an excited electronic state

Ultraviolet absorption spectrum has been observed of triethylenediamine (1,4 diazabicyclo[2.2.2]octane) ($\text{D}{}_{\mathrm{<mtext>3</mtext><mtext>A</mtext><mtext>?</mtext>}}$) vapor in the 2200–2600 Å region, and an analysis has been made of its vibrational structure. The vibronic 0-0 transition was determined to be at 2513.65 Å (39782.8 cm^?1), and in the 2540–2590 Å region there were four hot bands found: two from the a₁′-type vibrational levels and two from the a₂″-type vibrational levels of the ground electronic state. The fine structures of these hot bands were examined with 0.49 Å/mm dispersion (slit width = 50 μm). For each of the two a₂″-type hot bands, a progression with 30 ～ 40 cm^?1 spacings was observed; whereas, no such progressions were found for the a₁′-type hot bands, in which absorption peaks are much more concentrated within narrow ranges. These progressions were attributed to a large-amplitude twisting motion of triethylene-diamine molecule. For explaining the whole energy-level structure, another large-amplitude motion, has been postulated. That is a double-minimum deformation motion along the molecular axis; in each minimum, one of the two NC₃ umbrellas is half-way open and the other NC₃ umbrella is half-way closed. The height of the potential barrier between these two minima has been estimated to be 1586 cm^?1.     

Thermal Emission Spectrum of the Cobalt Monobromide Molecule

ABSTRACT

The thermal emission spectrum of the CoBr molecule has been photographed for the first time in the spectral region 4200–6000 Å using the high-temperature excitation technique and the 2-meter plane grating spectrograph (PGS-2). The spectrum has been recorded at a reciprocal linear dispersion of 7.3 Å/mm. About 203 red degraded and line-like bands have been recorded, out of which 172 are entirely new. The observed bands have been classified into 31 systems, of which 23 are entirely new. The vibrational analyses have been carried out using band head measurements and the Deslandre table. The ground state of the CoBr molecule is found to be ³Φ with the vibrational constants 318.3, 329.5, and 332.7 cm^?1.     

The Absorption Spectrum of UF6, from 2000 to 4200 Å

The absorption spectrum of UF₆ between 3400 and 4200 Å, is well-documented,^(1–3) but the region below 3400 Å has not been studied in any detail. We present here a spectrum of UF₆ between 2000 and 4200 Å that shows significant structure below 3400 Å. The absorption in this region must be observed at very low pressures and relatively short path lengths.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

Laser optogalvanic and emission spectrum of N2 in the 5400–6150 Å region

Laser optogalvanic (LOG) and emission spectra of the N₂ molecule have been recorded at different discharge voltages and gas pressures in the spectral region 5400–6150 Å. It is observed that in the optogalvanic spectrum bands belonging to several systems develop extensively. Under the present discharge conditions bands of the first positive system are predominant. The variation of the signals with pressure and voltage in the two cases is discussed.     

The ultraviolet absorption spectra of GeO in rare gas matrices

The absorption spectra of GeO isolated in rare gas matrices have been investigated in the wavelength region 1150–3000 Å using the 2.5-GeV synchrotron in Bonn as a continuum light source. Two vibrational progressions of bands have been found in each of the matrices, in neon, argon, krypton, and xenon. These progressions are situated in the regions 2400–2700 and 1800–2100 Å. They have been analyzed as corresponding to gas-phase bands of the A¹Π-X¹Σ⁺ and the E¹Σ⁺-X¹Σ⁺ systems, respectively. Absorption lines of matrix-isolated GeO were also found in the region 1180–1500 Å.     

Excitation and Emission Spectra of Cs2NaLnCl6 Crystals Using Synchrotron Radiation

ABSTRACT

The visible emission and vacuum ultraviolet excitation spectra of the series Cs₂NaLnCl₆ (Ln = Y, Nd, Sm, Eu, Tb, Er, Yb) and Cs₂NaYCl₆:Ln³⁺ (Ln = Sm, Er) have been recorded using synchrotron radiation at room temperature, and in some cases at 10 K. The excitation spectra comprise features associated with charge transfer, excitation from the valence to conduction band, and impurity bands. No d–f emissions were observed for these Ln³⁺ ions, so that the emission bands comprise intraconfigurational 4f ^N –4f ^N transitions and impurity bands, whose natures are discussed. Theoretical simulations of the f–d absorption spectra have been included. The comparison with data from the synchrotron at Desy enables a comprehensive account of the ground (or vibrationally excited ground for Ln²⁺) states of the Ln³⁺ 4f ^N , Ln³⁺ 4f ^N?15d, and Ln²⁺ 4f ^N+1 configurations relative to the valence and conduction bands of Cs₂NaLnCl₆, for which the band gaps are between 6.6 and 8.1 eV.     

Laser characteristics of KCL:O-2

Amplified spontaneous emission and laser action have been observed at 77 K in KCL crystals containing the superoxide ion (O^-₂). The laser operates in two bands of width ～50 Å centered at 6350 Å and 5984 Å. These bands are the (lattice) phonon sidebands of vibronic transitions of the superoxide ion. At lower temperatures (～6 K) amplified spontaneous emission is observed in the zero phonon line at 6294 Å.     

Raman spectroscopic study of the antimonate mineral lewisite (Ca,Fe, Na)2(Sb,Ti)2O6(O,OH)7

The mineral lewisite, (Ca, Fe, Na)₂(Sb, Ti)₂O₆(O, OH)₇, an antimony-bearing mineral, has been studied by Raman spectroscopy. A comparison is made with the Raman spectra of other minerals, including bindheimite, stibiconite, and roméite. The mineral lewisite is characterised by an intense sharp band at 517 cm^?1 with a shoulder at 507 cm^?1 assigned to SbO stretching modes. Raman bands of medium intensity for lewisite are observed at 300, 356, and 400 cm^?1. These bands are attributed to OSbO bending vibrations. Raman bands in the OH stretching region are observed at 3200, 3328, 3471 cm^?1, with a distinct shoulder at 3542 cm^?1. The latter is assigned to the stretching vibration of OH units. The first three bands are attributed to water stretching vibrations. The observation of bands in the 3200–3500 cm^?1 region suggests that water is involved in the lewisite structure. If this is the case then the formula may be better written as (Ca, Fe²⁺, Na)₂(Sb, Ti)₂(O, OH)₇ xH₂O.     

Equation of state and thermal expansivity of LiF and NaF

The high-pressure and high-temperature behaviors of LiF and NaF have been studied up to 37 GPa and 1000 K. No phase transformations have been observed for LiF up to the maximum pressure reached. The B1 to B2 transition of NaF at room temperature was observed at ～28 GPa, this transition pressure decreases with temperature. Unit-cell volumes of LiF and NaF B1 phase measured at various pressures and temperatures were fitted using a P–V–T Birch–Murnaghan equation of state. For LiF, the determined parameters are: α₀ = 1.05 (3)×10^?4 K^?1, dK/dT = ?0.025 (2) GPa/K, V ₀ = 65.7 (1) Å³, K ₀ = 73 (2) GPa, and K′ = 3.9 (2). For NaF, α₀ = 1.34 (4)×10^?4 K^?1, dK/dT = ?0.020 (1) GPa/K, V ₀ = 100.2 (2) Å³, K ₀ = 46 (1) GPa, and K′ = 4.5 (1).     

Laser induced infrared fluorescence of Cs2 and Rb2

Laser induced cross fluorescence of Cs₂ and Rb₂ molecules in the infrared region (1.0–1.6 μm) has been observed using several exciting wavelengths from an argon-ion laser and a tunable cw dye laser. New emission bands have been observed. The lower states of these bands have gerade symmetry and therefore have heretofore escaped observation by conventional absorption spectroscopy.     

Optical absorption spectra of PtO and Pt2 in rare-gas matrices

The diatomic molecules, PtO and Pt₂, as well as atomic Pt, were isolated in Ar and Kr matrices at a temperature of ca.12K. The absorption spectra of these species were photographed in the wavelength region 2500–9000 Å. Probably three systems of PtO were observed but none of them seemed to correspond to the earlier analyzed intense systems of gaseous PtO having a ¹Σ state, designated X¹Σ, as their common lower state. The assumption that this state should be the ground state of PtO is thus rather uncertain. A single progression of sharp bands in the near-infrared spectrum was ascribed to the dimer Pt₂. In addition, some absorption lines due to Pt atoms were found in the ultraviolet region.     

UV–visible,infrared absorption spectra of undoped and TiO2-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and TiO₂-doped lead phosphate glasses were prepared. Ultraviolet (UV)–visible and Fourier transform-infrared (IR) absorption spectra of the prepared samples were measured before and after being subjected to doses of 30 and 60 kGy of gamma irradiation. The parent undoped lead phosphate glass reveals charge transfer UV absorption bands which are attributed to the presence of unavoidable iron impurities contaminated within the raw materials used for the preparation of the glasses and the sharing of divalent lead (Pb²⁺) ions. Experimental spectral data indicate that the doped titanium ions are involved in such glasses in two valences, namely the trivalent and tetravalent states. The predominant trivalent titanium (Ti³⁺) ions are characterized by its purple color and exhibiting two visible absorption bands at about 500–550 and 700–720 nm. The lesser tetravalent titanium (Ti⁴⁺) ions belong to the d⁰ configuration and generally exhibit only an UV absorption band. Spectral data show that gamma irradiation causes noticeable changes in the undoped and TiO₂-doped samples in the UV range while the effects are limited in the visible range. The observed changes in the UV region are attributed to photochemical reactions while TiO₂-doped samples show retardation or shielding toward continuous gamma irradiation together with the sharing of heavy Pb²⁺ ions. IR absorption spectra reveal the vibrations of several phosphate groups including the metaphosphate chains as the main structural building units together with the possible Pb?O vibrations.     

Electronic Transition Moment Variation in the C2Π–X2Σ+ System of Boron Monoxide

The extensive band system belonging to the C²Π_r–X²Σ⁺ transition of boron monoxide (BO) molecule lying in the vacuum ultraviolet region (150–230 nm) has been recorded in emission in a hollow cathode glow. A few new bands involving high v′ levels of C state have been observed. The Franck–Condon factors and r‐centroids were computed for the C–X system. By correlating the measured intensities to theory, the (relative) variation of the C–X electronic transition moment with internuclear separation was examined.     

Study of the precipitation behavior of NaCl:Pb and KCl:Pb by optical spectroscopy2

The aggregation and precipitation behavior of lead in NaCl and KCl crystals has been systematically investigated by absorption and luminescence spectroscopy. For NaCl, absorption bands at 265 and 285 nm have been identified which correspond to intermediate stages in the formation of a double band (262–266 nm) associated with PbCl₂ precipitates. The kinetics of growth during ageing as well as the thermal annihilation behavior have been obtained for all bands. The emission spectra for excitation at those absorption bands have also been determined. For KCl, absorption bands at 265 and 280 nm develop during ageing at 160 and 200°C and their growth-rate is markedly enhanced by plastic straining. Their emission spectra involve a main band at $\text{\$}\text{?}$550 nm. In contrast to NaCl, no stage has been found where those absorption bands feed into a final band, which could be associated with PbCl₂ precipitates.     

The optical spectrum of the doubly charged molecular nitrogen ion: Rotational analysis of the (0-0) and (1-1) bands of the D1Σu+-X1Σg+ transition of N22+: Comparison of observations with Ab-initio calculation results

Emission spectra obtained in the 1550–1650 Å region with a 10-m vuv spectrograph are conclusively assigned to the N₂²⁺ ion. The 1589-Å band, previously observed by Carroll, and a new band of the same system, have been rotationally analyzed. Ab-initio calculations have been performed which support the assignment of these two bands to the D¹Σ_u⁺-X¹Σ_g⁺ system. The calculations also explain the observed breaking-off points in the branch structure as well as weakening and broadening of the other expected bands. These phenomena arise from electron configuration changes and perturbation effects in the ground state.     

The impurity-induced luminescence of RbMnF3

The impurity-induced luminescence of RbMnF₃ has been studied in the temperature range, 4–120 K. Multimagnon sidebands of impurity-induced Mn²⁺ emission lines have been detected spanning the spectral range, 5515–5960 Å. The broad emission bands, which peak at 5750 Å and 6440 Å, have been attributed to phonon-assisted transitions from two impurity-induced Mn²⁺ traps of different depths. Pulsed luminescence measurements indicate that the quenching of the shallow trap emission is by a thermal activation to the E1 exciton level whereas the quenching of the deeper trap emission is by a multiple phonon decay. The coupling between Mn²⁺ ions is strong enough to support a detectable transfer of excitation between these two traps.The results of this research also include the observation in absorption of the E1 exciton line and its 1-magnon and possible 2-magnon sidebands.     

Optical and electrical properties of some sulphates doped with cobalt

Doubly ionized cobalt ion which has a ⁴F ground state exhibits several optical bands in orthorhombic sulphates. In view of the low symmetry, many degenerate states split and at low temperature (77°K) well resolved bands have been observed which enable the detailed calculation of the crystal field parameters in orthorhombic symmetry.Electrical conductivity measurements in pure potassium and ammonium sulphates show only the extrinsic unassociated region while in cobalt doped crystals, extrinsic as well as association regions are observed. Three distinct regions with slopes 0·86, 1·2 and 0·5 eV are obtained in cobalt doped K₂SO₄.X-irradiated pure crystals give two prominent bands at 2200 and 3300 Å which are attributed to SO₃^? and SO₂^?. Divalent cobalt doped crystals give additional bands at 2100 and 3100 Å. These bands are attributed to Co⁺ in different surroundings. Three ESR lines with ‘g’ values 2·042, 2·02 and 2·004 are obtained in support of the assignments.     

AgI nanostructure development in sputter-disordered and Al-doped Ag films probed by XRD,SEM, optical absorption and photoluminescence

By use of thermal evaporation and rf magnetron sputtering 300 and 500 Å thick Ag and Ag (Al) films were prepared. γ-AgInanoparticles were formed during (a) short time (2–5 min) iodization of undoped thermally evaporated Ag films, (b) longer time (12 h) iodization of undoped rf sputtered Ag films and (c) short time (2–15 min) iodization of thermally evaporated Ag_0.95Al_0.05 and Ag_0.90Al_0.10 films of 500 and 300 Å thickness respectively. Both rf sputtered and Al doped Ag films yielded ～20 to ～60 nm sized γ-AgI particles upon iodization. Optical absorption spectra reveal Z_1,2 and Z₃ exciton transitions with increased broadening of γ-AgI nanoparticles, suggesting the effect of disorder produced during film formation. Blue shift observed with increasing film thickness could be the effect of decreasing particle size, thereby increasing the quantum confinement effects. Photoluminescence studies show that the donor-acceptor recombination rate, enhanced by 25% for Ag_0.95Al_0.05I film relative to that of undoped AgI, is due to the tight binding of Al to surface defect sites.