Quenching of SO2 phosphorescence by a magnetic field

Phosphorescence excitation spectra of the ã³B₁← [Xtilde]¹A₁ transition of SO₂ were measured in the absence and presence of a magnetic field (B = 0?44 T², P(SO₂) = 0?7 Torr). The absorption and phosphorescence excitation spectra of the ã³B₁← [Xtilde]¹A₁ transition of SO₂ measured in the absence of a magnetic field show that the relative intensity of the bands of the phosphorescence excitation spectrum is smaller than the relative intensity of the corresponding bands of the absorption spectrum beginning with the (0, 2, 0) band. In the presence of a magnetic field, the intensity of the phosphorescence excitation band falls, for ν_exc> 26400 cm^-1. Under the direct excitation of the ã³B₁← [Xtilde]¹A₁ transition, the dependence of the magnetic quenching of the SO₂ phosphorescence on the excitation frequency (ν_exc) was studied at P(SO₂) = 0?7 Torr and B = 0?44 T. The dependence of the magnetic field effect on ν_excshows that only the vibrationally excited levels of the ã³B₁ state are sensitive to an external magnetic field. The magnetic field strength and the pressure dependence of the magnetic field effects were studied under indirect excitation of the ã³B₁← [Xtilde]¹A₁ transition at λ_exc = 308 nm. The magnetic field and the pressure dependence were investigated for pure SO₂ and for SO₂ + RH (RH n-C₅H₁₂) mixtures. It was found that the magnetic field effect was saturated at B ? 0?25 T. The saturation value (Gr = l(0?3 T)/l(0)) increases with increasing gas pressure. The magnetic field, the pressure and the excess vibrational energy (ν_excess) dependence of the magnetic quenching of SO2 phosphorescence show that the data observed can be explained by an indirect mechanism within the framework of a low level density approximation.     

Ultraviolet laser-induced fluorescence spectrum of fluorochlorocarbene in solid argon

CFCl has been produced for spectral investigation by matrix reactions of alkali metal atomic beams with CFCl₃ in argon followed by rapid quenching to 15°K on a tilted copper wedge. When these samples were irradiated with near uv light from a krypton ion laser, a very intense, highly structured fluorescence spectrum was observed. This emission system extended from about 25 000 cm^?1 to 15 000 cm^?1 and peaked in intensity at about 22 000 cm^?1. The three most intense progressions are assigned to transitions from a common excited state to ground state levels (0v₂0), (1v₂0) and (1v₂1). New molecular constants determined from these progressions include $\text{ω}{}_2{}^0\text{= 446}\text{cm}{}^{\mathrm{?1}}$, x₂₂ = ?1.2 cm^?1, x₁₂ = ?3 cm^?1, x₂₃ = ?4 cm^?1, and x₁₃ = ?6 cm^?1. CFCl was also produced by in situ photolysis of CFCl₃ using laser plasma emission and by alkali metal atom reactions with CF₂Cl₂, CF₂ClBr, and CHFCl₂.     

Lichtausbeute von α-Teilchen in kristallinem und dampfförmigem Anthrazen

The light output,S _v by α-particles stopped in anthracene vapour has been measured as a function of vapour pressure (10–700 mm Hg) and temperature (250°C–385°C). The comparison of the results for an idealised vapour neglecting collisions with the light output,S _c, from anthracene crystals by α-particles impinging parallel to thec′-axis yields the unexpected results: S_v(8.78 MeV)/S_c(8.78 MeV)=0.46±0.05 andS _v(6.05 MeV)/S _c(6.05 MeV)=0.57±0.08. A simple model assuming quenching by collisions of the vapour molecules could explain the observed dependence of the light output on the vapour pressure at fixed temperature. The path lengthsR _v of α-particles in anthracene vapour were determined to be R_v(8.78 MeV)=(9.0±0.6) mg/cm²,R _v(6.05 MeV)=(4.9±0.6) mg/cm² and the ratio of the light output by the two different α-energiesS _v(8.78 MeV)/S _v(6.05 MeV)=1.42±0.2.     

The ground state of molecular hydrogen

The v = 0?0 quadrupole spectrum of H₂ has been recorded using a 0.005-cm^?1 resolution Fourier transform spectrometer. The rotational lines S(1) through S(5) are observable in the spectra, in the region 587 to 1447 cm^?1. The spectral position for S(0) was also obtained from its v = 1-0 ground-state combination difference. The high accuracy of the H₂ measurements has permitted a determination of four rotational constants. These are (in cm^?1) B₀ = 59.33455(6); D₀ = 0.045682(4); H₀ = 4.854(12) × 10^?5; L₀ = ?5.41(12) × 10^?8. The hydrogen line positions will facilitate studies of structure and dynamics in astrophysical objects exhibiting infrared H₂ spectra. The absolute accuracy of frequency calibration over wide spectral ranges was verified using 10-μm CO₂ and 3.39-μm CH₄ laser frequencies. Standard frequencies for 5-μm CO were found to be high by 12 MHz (3.9 × 10^?4 cm^?1).     

Multiple photon excitation of the v2 + v6 combination band of SF6 in a bulk and in a pulsed free jet

Multiple photon excitation of the v₂ + v₆ combination band of SF₆ in a bulk at T ≈ 295 K and cooled in a pulsed free jet up to T_V ≈ 160 K and T_R ≈ 40 K by a pulsed TEA CO₂ laser has been investigated. Obtained results are compared with the data on the v₃ vibration excitation. At exciting energy fluences ø = 0.1?2.5 J cm^-2 the levels in the region of the discrete vibrational states (v=3?5) are found mainly to be excited. Multiphoton absorption spectra at room temperature have a sharp resonant structure. The fraction of interacting molecules is considerably (3–7 times) less compared than that for the case of v₃ vibration excitation. Multiphoton absorption of the v₂ + v₆ and v₃ vibrations of SF₆ is shown to be proportional to the dipole moments of the corresponding transitions.     

Exciton system heating in ZnSe single crystals under laser excitation

The way to determine the effective temperature of the excitonic system from the study of the edge luminescence high energy region is motivated. Experimental data on the exciton heating in ZnSe single crystals under laser excitation are presented. The effective temperature of excitons T_x has reached 158 K at the lattice temperature T_L = 77 and the peak excitation intensity 2.7 MW cm^?2 (hv₀ = 3.50), while the excess temperature of the excitons (T_x ? T_L) increases as a square root of the pump intensity. Exciton-hot-electron, exciton-hot-photon, exciton-exciton interactions and excitonic Auger process are considered as possible causes of the exciton system heating.     

Far-infrared laser magnetic resonance spectra of the PH and PD radicals in X3Σ−

Far-infrared laser magnetic resonance (LMR) spectra of PD in the ground vibronic state (X³Σ^?, v = 0) were observed using the 570.6-, 380.6-, 287.3-, 232.9-, 191.6-, and 164.6-μm laser lines as sources, and the v = 1 spectrum was also observed with the 392.1-μm laser line. By combining the present results with mid-infrared LMR and optical spectroscopic data already reported, the molecular constants of PD in X³Σ^? were refined as follows: B₀ = 4.362 8675(77), D₀ = 0.000 118 03(24), λ₀ = 2.208 48(57), γ₀ = ?0.039 900(34), B₁ = 4.269 248(65), λ₁ = 2.209 5(10), γ₁ = ?0.038 82(21), and ν₀ = 1653.284 91(51), all in cm^?1 with 3σ in parentheses. The ³¹P hyperfine coupling constants were determined to be α_P = 0.004 330(39) and β_P = ?0.005 312(32) for the v = 0 state and α_P = 0.004 66(40) and β_P = ?0.004 79(69) for the v = 1 state, again in cm^?1 with 3σ in parentheses. The far-infrared LMR spectra of PH in the X³Σ^?, v = 0 state were measured on five new laser lines, and an analysis of the observed spectrum combined with that already reported yielded molecular constants much improved in precision. Using the results on both PD and PH, the equilibrium structure and the potential constants up to the fourth order were derived, where allowance was made for adiabatic and nonadiabatic corrections: $\text{r}{}_{\mathrm{e}}{}^{\mathrm{BO}}\text{= 1.42140(22)}\text{A}\text{?}$, ω_e(PH) = 2366.79(16) cm^?1, a₁ = ?2.3797(18), and a₂ = 3.461(14).     

Surface-enhanced Raman spectroscopy of electrochemically characterized interfaces; potential dependence of Raman spectra for thiocyanate at silver electrodes

Surface-Enhanced Raman Spectra have been obtained for thiocyanate anions at silver electrodes following an oxidation-reduction cycle (ORC) as a function of electrode potential and electrolyte composition and compared with the extent of thiocyanate adsorption determined under the same conditions from differential capacitance-potential data. A spectrograph equipped with an optical multichannel analyzer (OMA) detector and a scanning spectrometer were used to make the Raman measurements. Spectra were obtained over the frequency range 100–2200 cm^?1, where all three normal vibrations, CN stretching (v_CN, 2090–2120 cm^?1), CS stretching (v_CN, 735 cm^?1), NCS angle bending (δ_NCS, 450 cm^?1) occur, along with a low frequency vibration attributed to a metal-ligand stretching mode (v_ml, 200–215 cm^?1) arising from a silver-sulfur surface bond. Both v_CN and v_ML decreased in frequency as well as intensity as the potential was made more negative in the region ?100 to ?700 mV versus Ag/AgCl for bulk thiocyanate concentrations of one millimolar and above, even though the thiocyanate surface concentration remained close to a monolayer throughout. By means of rapid time-resolved spectral measurements following potential steps using the OMA, the decrease of the intensity and frequency of the v_CN mode with increasing negative electrode potential was separated into a rapid “reversible” component and a slower “irreversible” decay. The latter component is attributed to the decay of Raman-active sites associated with the dissipation of metastable silver clusters formed during the ORC, that are prevented from rearranging at more positive potentials due to the presence of surrounding anionic adsorbate.     

Rotational analysis and radiative lifetime measurement on the 2B1 (K′ = 0) excited state of NO2 with v′2 = 6, 7, 8, and 9

The rotational structure of the ²B₁ (K′ = 0) subbands of NO₂ with v′₂ = 6, 7, 8, and 9 were analyzed by means of the time-gated excitation spectrum. The excitation spectrum monitored at ν₂, 2ν₂, or 3ν₂ fluorescence band was fairly simplified in comparison to its corresponding absorption spectrum. The band origins and rotational constants are evaluated from the observed data: ν₀ = 20205.0 cm^?1, $\text{B}\text{′ = 0.374}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 6; ν₀ = 21104.4 cm^?1, $\text{B}\text{′ = 0.374}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 7; ν₀ = 22001.9 cm^?1, $\text{B}\text{′ = 0.375}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 8ν₀ = 22898.0 cm^?1, $\text{B}\text{′ = 0.375}\text{cm}{}^{\mathrm{?1}}$ for v′₂ = 9. The value of $\text{B}\text{′}$ extrapolated to v′ = 0 is 0.370 cm^?1. This value corresponds to the bond length of 1.19 Å. Fluorescence decays of these excited levels were also studied. Radiative lifetimes obtained by extrapolation to zero pressure from the $\text{1}\text{τ}\text{– P}$ plots were 25–40 μsec. The short-lived excited levels previously reported by some authors were not found.     

Rate coefficient and transition probability of XeO

Rate coefficients of XeO(¹S) at various vibrational levels (v = 0, 1 and 2) were observed by measuring absolute intensities of the spectrum in the low-pressure d.c. glow of an Xe-O₂ mixture discharge. The association coefficients at the various levels are K_a0 = 2.4×10^-34 cm⁶ at v = 0, K_a1 = 1.1 × 10^-34 cm⁶ atv = 1, and K_a2 = 9.1 × 10^-35 cm⁶ at v = 2. The transition probability from XeO(¹S)₀ to $\text{XeO(}{}^1\text{D)u}$ is estimated to be A₀ = 1.3 × 10⁵ sec^-1.     

Ionoluminescence and photoluminescence studies of Ag ion irradiated kyanite

Ionoluminescence (IL) of kyanite single crystals bombarded with 100 MeV swift Ag⁸⁺ ions with fluences in the range 1.87-7.5×10¹¹ ions/cm² has been studied. A pair of sharp IL peaks at ∼689 and 706 nm along with broad emission in the region 710-800 nm are recorded in both crystalline and pelletized samples. Similar results are recorded in Photoluminescence (PL) of pelletized kyanite bombarded with same ions and energy with fluences in the range 1×10¹¹-5×10¹³ ions/cm² with an excitation of 442 nm laser beam. The characteristic pair of sharp emission peaks at 689 and 706 nm in both IL and PL is attributed to luminescence centers activated by Fe²⁺ and Fe³⁺ ions. The reduction in IL and PL bands intensity with increase of ion fluence might be attributed to degradation of Si-O (2ν₃) bonds, present on the surface of the sample.     

Infrared tunable diode laser spectroscopy of the Δv = 2 band of 7Li127I

The high-resolution infrared spectrum of the Δv = 2 transitions of ⁷LiI has been measured at temperatures near 1050 K. The observations include vibrational transitions ranging from 2-0 to 10-8. The data were fit to a set of Dunham potential constants complete through the a₆ term, from which the Dunham rovibrational constants were calculated. The band centers for the v = 1-0 and v = 2-0 transitions were determined to be 491.17398 ± 0.00026 cm⁻¹ and 976.73042 ± 0.00038 cm⁻¹, respectively.     

Determination of relaxation times of ground electronic state vibrational levels of mixed molecular crystals

The stimulated emission spectra of mixed molecular crystals were investigated with the Nd glass lasser third harmonic excitation at 4.2 K. Napthalene crystals doped with β-naphthyl-n-biphenylyl ethylene and dibenzyl doped with naphthacene in various concentrations were studied. Relaxation times of the ground state vibrational levels in mixed molecules were obtained by use of the dependence of stimulated emission intensity upon excitation energy for naphthacene in dibenzyl τ₁ of the vibrational level at 317 cm^-1 was ～ 3 × 10^-9 s; for β-naphthyl-n-biphenylyl ethylene in naphthalene τ₁ of the 1629 cm^-1 vibrational level was ～ 10^-10 s.     

Intensity detection of picosecond ruby laser pulses by two photon absorption

The peak intensity of single picosecond light pulses from a mode locked ruby laser and its second harmonic is detected by two photon transmission measurements. The two photon absorption coefficients α⁽²⁾ of the applied crystals CdS and KI are measured (α⁽²⁾_CdS (14400 cm^-1) = 19 cm/GW, α⁽²⁾_KI (28 800 cm^-1) = 8 cm/GW) and calibration curves are presented.     

Infrared spectrum of stannous oxide (SnO)

A tunable diode laser has been used to measure the infrared spectrum of stannous oxide (SnO) in the gas phase between 830 and 868 cm^?1. Measurements of the v = 1-0, 2-1, 3-2, and 4-3 transitions have been made at temperatures ranging from 930 to 1150°C. Over 175 infrared transitions of the nine most abundant SnO isotopic species have been combined with microwave measurements reported by others in a single least-squares analysis of the data to yield a set of eight Dunham coefficients for the X¹Σ⁺ state of SnO. The data have also been fit by a nonlinear least-squares procedure to obtain B_e, ω_e, and the first five Dunham potential constants. The band center for the vibrational transition of ¹²⁰Sn¹⁶O is found at ν₀ (v = 1?0) = 814.70249 ± 0.00027 cm^?1.     

High resolution interferometric fourier transform infrared spectroscopy in supersonic free jet expansions: N2O,CBrF3 and CF3I

Continuous flow supersonic jet expansions of neat nitrous oxide N₂O, bromotrifluoro methane CBrF₃ and trifluoroiodo methane CF₃I have been investigated by FTIR absorption spectroscopy in the 8–9 μm region at high resolutions of 0.004 and 0.0024 cm⁻¹ (fwhm). Rotational temperatures of 26 K for N₂O, 45 K for CBrF₃ and 50 K for CF₃I have been determined from the spectra. For the v₁ band of N₂O the contribution of background gas to the FTIR spectrum and to the nonlinearity of Boltzmann plots has been evaluated. New spectroscopic parameters have been determined for the v₁ and v₁ + v₆ − v₆ bands of C⁷⁹BrF₃ and C⁸¹BrF₃ with band centers v⁻⁰₁ (C⁷⁹BrF₃) = 1084.7690(1),~ v⁰₁ (C⁸¹ BrF₃) = 1084.5214(1), ~v⁰₁₆₆(C⁷⁹BrF₃) = 1083.5292(2) and ~v⁰₁₆₆ (C⁸¹BrF₃) = 1083.2846(2) cm⁻¹ as well as for the v₄ band of ¹²CF₃I with band center ~v⁰₄ = 1187.6275(1) cm⁻¹. The results are important for IR-multiphoton excitation, laser chemistry, and atmospheric chemistry and spectroscopy.     

Photoluminescence and gain spectroscopy of highly excited epitaxial GaN-layers

The spectra of photoluminescence and optical gain of GaN have been measured at low temperatures under N₂-laser excitation.At low excitation levels (I _exc10⁴W cm^–2) we observe free and bound exciton recombination. At intermediate excitation (I _exc10⁵W cm^–2), inelastic exciton-exciton scattering processes show up. At the highest excitation levels (I _exc10⁶ W cm^–2) we report here for the first time the emission from an electron-hole plasma.     

The pure rotational atmospheric lines of hydroxyl

Pure rotational line positions of the hydroxyl radical (OH) have been calculated for all vibrational levels expected in the earth's atmosphere (v = 0–9) and for lower rotational quantum numbers J″=0.5–12.5. These positions have been tabulated and compared with those derived from energy levels obtained from precise near-i.r. vibration-rotation bands and show good agreement for low J″ values. A tentative identification has been made of three v = 0 lambda-type doublets in a high-resolution far-i.r. (30–120 cm^-1) emission spectrum of the atmosphere obtained at 30 km from a balloon-borne platform. Line strength (S_J′J″) and integrated intensity (S_q cm^-2atm^-1) values have been derived for these pure rotational transitions as an aid to further work and instrument design.     

Electroabsorption in TlInS2

Electroabsorption spectra of single crystals have been studied near the fundamental absorption edge at 77 and 300 K. At 300 K two positive peaks (2.34 and 2.42 eV) and a negative peak (2.38 eV) are observed in the electroabsorption spectrum. At liquid-nitrogen temperature a fine structure corresponding to the formation of a parabolic exciton (2.503 eV) is observed.Values of the width of the forbidden gap E_g, the n = 1 exciton positions, the exciton activation energy ΔE_b, the effective Bohr radius a_exc, the reduced effective mass of an electron-hole pair μ, and the exciton ionization field F(E_g = 2.535 eV, E_exc = 2.503 eV, E_b = 32 meV, $\text{a}{}_{\mathrm{<mtext>exc</mtext>}}\text{=}\text{28}\text{A}\text{A;}\text{;}$;, μ = 0.15 m₀, and F = 1.2 × 10⁵ V cm^-1) have been determined from the electroabsorption spectrum.     

Doppler-limited dye laser excitation spectrum of the C2 Swan band (v′ − v″ = 1 − 0)

The dye laser excitation spectrum of the Swan band (v′ ? v″ = 1 ? 0) has been observed with Doppler-limited resolution. The C₂ molecule was generated by the reaction of microwave discharge products of CF₄ with CH₄. The high sensitivity of laser excitation spectroscopy has enabled us to observe not only $\text{ΔΩ}\text{= 0}$ transitions, but also $\text{ΔΩ}\text{= ± 1}$ transitions and to determine molecular constants including the spin-orbit coupling constant for both the d³Π_g and a³Π_u states. The parameters thus obtained for a³Π_u were favorably compared with those previously obtained from the Ballik-Ramsay band. The present results on the d³Π_gv = 1 state were combined with those of an earlier Fourier spectroscopic study on the Swan band (v′ ? v″ = 0 ? 0) to derive equilibrium molecular constants for the d³Π_g state. The contributions of the spin-rotation interaction and the centrifugal correction for the spin-orbit coupling to the energy levels in a ³Π state have been discussed in detail.