Radiative decay of the metastable quartet state of copperporphin

In CuP the low temperature luminescence originates from eight transitions between a quartet (M = ±3/2, ±1/2) and a doublet (M′ = ±1/2) with M and M′ denoting the (approximate) eigenvalues of the spin angular momentum S_z along the fourfold axis. Here we report (1) the selection rules governing the polarizations of the transitions; (2) the zero-field splitting ξ between the ±3/2 and ±1/2 components of the quartet for CuP in an n-octane crystal (ξ = 1·1 ± 0·2 cm^-1); (3) a photo-selection experiment on CuP in an isopentane glass from which it is concluded that the ratio of in-plane to out-of-plane polarization in the 0-0 band at 2·1 K amounts to an intensity ratio I _‖/I _⊥ ≈ 2. The implications of these results for the different SOC pathways are analysed.     

Line strength and halfwidth measurements from far infrared absorption spectra: Carbon monoxide

A method for deriving Lorentzian line shape parameters (line strengths and halfwidths) from absorption spectra taken at two different path lengths is discussed. Far i.r. absorption spectra of carbon monoxide are analysed to yield line strengths and halfwidths for the rotational transitions J″ = 3 through J>″ = 9. Experimental errors are discussed, and the value for the dipole moment derived from the line strengths, 0·108±0·005 D, is in agreement with the microwave value within experimental uncertainty. The Lorentzian halfwidths are compared, where appropriate, with two recent determinations of these quantities. Lorentzian halfwidths are also derived from absorption spectra taken at long path length using theoretical line strengths based upon μ_co = 0·112D.     

“Forbidden” millimeter-wave transitions in arsine

A millimeter-wave spectrometer having a sensitivity of 4 × 10^?10 cm^?1 in the 2-mm region has been used for observation of the “forbidden” transitions J → J, K = ±4 → ±1 and J → J, K = ±5 → ±2 in AsH₃. A comprehensive computer analysis was made of the frequencies measured in this work together with available microwave frequencies of other transitions. This analysis provides accurate values of the rotational constants, nuclear quadrupole couplings, and effective structural parameters of the molecule. The spectral constants B₀ and C₀ (in MHz) are 112 470.597 and 104 884.665, respectively.     

High resolution FTIR spectra of AsD3 in the 20-1000 cm−1 region. The ground, 98, v2 = 1 and v4 = 1 states

The pure rotational spectrum of the near-spherical oblate symmetric top AsD₃ has been recorded in the 20–120cm^?′ region with a resolution of 2.3 × 10^?3 m^?1 employing an FT interferometer. Rotational transitions with 5 ? J ? 29 and 0 ? X ? 25 of the ground state (GS) and the v₂ = 1 and v₄ = 1 excited states have been assigned. Splittings were observed for the GS, 98, K = 3 and 6 levels, the K = 3 levels of v₂ and the kl = ?2, 1, 4 and 7 levels of v₄. Furthermore the x,y Coriolis coupled v₂ and v₄ bands, v ⁰ ₂ = 654.4149cm^?1, and v ⁰ ₄ = 714.3399 cm^?1, have been examined with a resolution of 2.4 × 10^?3 cm^?1, and ca. 2500 allowed and 336 ‘forbidden’ lines with J′_max = 31 and K′_max = 28 have been assigned. Appropriately weighted GS data comprising FIR lines, allowed and ‘forbidden’ (up to ΔK = ±6) GS combination differences, mmw data, and ΔJ = 0, ΔK = ±1 distortion moment transitions were fitted together, and GS parameters complete through H parameters have been determined. Two different reductions of the Hamiltonian, either with ΔK = ±6 (h₃) or ΔK = ±3 (ε) off-diagonal elements, have been employed. Equivalence of these reductions up to J = 22 was established while for J > 22 the ε reduction is superior. The v₂ and v₄ data have been fitted with two equivalent models based on different reductions of the rovibrational Hamiltonian. In addition to the dominating x,y Coriolis resonance, ζ ^y ₂₄ 0.520, Δ(k ? l) = ±3 and ±6 interactions are important and were accounted for by the models. The transition moment ratio |M₄: M₂| =0.75 has been determined, with a positive sign of the product M ₂ζ ^y ₂₄ M ₄. An improved r₀ structure, r₀(AsD) = 1.51753 Å and α₀(DAsD) = 92.000°, has been determined.     

Energy and angular momentum transfer in atom-diatom collisions from polarized laser fluorescence

We report a study of collisional reorientation of diatomic lithium molecules by rare gas atoms using high resolution circularly polarized laser fluorescence. As in the case of I₂ we find that elastic collisions are very inefficient at reorienting Li₂ molecules and a selection rule ΔM′ _J = 0 appears to be in operation. Rotationally inelastic collisions, particularly those with argon, cause some degree of reorientation and are the result of relatively long range intermolecular interactions. Vibrational transfer features are more strongly depolarized. Optical pumping studies of oriented ¹Σ _g Li₂ molecules have yielded a cross section for inelastic transfer of 35 ± 15 Ų.     

M-dependence of collisional transfer of rotational energy in OCS mixtures

Collision-induced transitions between rotational levels of OCS in the ground vibrational state have been investigated by steady-state microwave double resonance, with the M sublevels separated by a Stark field. The (2 ← 1)_P-(1 ← 0)_S, (3 ← 2)_P-(1 ← 0)_S, and (4 ← 3)_P-(1 ← 0)_S systems have been studied for pure OCS and for mixtures with excess CH₃OH, He, and H₂. For four-level systems having dipolar connections (ΔJ = 1; ΔM = 0, ± 1; parity ± ? ?) between pump and signal levels, it is found for OCS and the OCS-CH₃OH mixture that the dipole-type ΔJ = 1 transitions always dominate the collisional transfer, but for the OCS-He and OCS-H₂ mixtures that ΔJ = 2 quadrupole-type transitions are dominant. For all four collision partners, significant ΔJ = 2 and ΔJ = 3 collisional transfer is observed in some systems, indicating the presence of high-order terms in the collisional interaction.     

Heterodyne frequency measurements on carbonyl sulfide near 1050 cm

Heterodyne techniques have been used to measure the frequency differences between carbonyl sulfide (OCS) absorption lines and CO₂ laser transitions. A tunable diode laser was used both to scan the OCS absorption spectrum and to provide a beat signal against a CO₂ laser. Frequency differences as great as 8.6 GHz were measured. Many different OCS hot-band transitions were measured near 1050 cm⁻¹, and the measurements on the 02⁰0-00⁰0 band have been extended to such high J levels (J′ = 86) that higher-order centrifugal distortion terms are needed to fit the data.     

A Partial Wave Analysis of the Reaction π+p→ (π+π−π0) Δ++ at 16 GeV/c

A partial wave analysis of the 3π-system has been performed for the reaction π⁺p→ (π⁺π^?π⁰) Δ⁺⁺ (1232) at 16 GeV/c. Beside the well-established A₂⁰ (1300), the resonant state ω* with isospin I = 0 and spin-parity J^P = 3^? decaying mainly into (?π) has been found. Its mass and width have been determined to be M = (1.71 ± 0.03) GeV and Γ = (0.22 ± 0.10) GeV. The cross section for the reaction π⁺p→ ω* (1700) Δ⁺⁺ (1232) is σ = (12 ± 6) μb.     

Variation of Br quadrupole coupling with isotopic substitution in methyl bromide

The J = 0 ← 1 transitions in CH₃⁷⁹Br (I), CH₃⁸¹Br (II), CD₃⁷⁹Br (III), and CD₃⁸¹Br (IV) were measured using a Stark-cell spectrometer constructed from C-band waveguide. High-resolution spectra yielded precise values for the bromine quadrupole coupling strength. Values obtained were eqQ(I) = ?577.08 ± 0.15 MHz, eqQ(II) = ?482.18 ± 0.15 MHz, eqQ(III) = ?575.66 ± 0.15 MHz, and eqQ(IV) = ?480.89 ± 0.15 MHz. The observed center frequencies for the J = 0 ← 1 transitions are ν₀(I) = 19136.35 ± 0.03 MHz, ν₀(II) = 19063.62 ± 0.03 MHz, ν₀(III) = 15429.23 ± 0.03 MHz, and ν₀(IV) = 15362.41 ± 0.03 MHz. A 0.26 ± 0.02% decrease in bromine quadrupole coupling is observed when the methyl group is fully deuterated. This is in agreement with, and supports interpretations given for, previous results on methyl chloride.     

Inelastic collision cross section of excited molecules

The (v′=6,J′=43) level in theB ¹Π _u electronic state of Na₂ has been selectively populated by excitation with the 4 880 Å line of the argon laser. Through collisions with He atoms energy is transferred to neighbouring rotational states in Na₂ and the density of these states is determined by observing fluorescence to electronic ground state. From previous measurement of the lifetime of theB ¹Π _u state and new measurements of the intensities of collision induced spectral lines as a function of He pressure, absolute collision cross sections for all rotational transitions up to ΔJ=±5 have been obtained. The total cross section for all rotational transitions observed is σ _rot ^total =65±15 Ų. Preliminary results about collision induced vibrational transitions are also presented.     

Photolysis rate coefficients in the upper atmosphere: Effect of line by line calculations of the O2 absorption cross section in the Schumann-Runge bands

A line by line (LBL) method to calculate highly resolved O₂ absorption cross sections in the Schumann-Runge (SR) bands region was developed and integrated in the widely used Tropospheric Ultraviolet Visible (TUV) model to calculate accurate photolysis rate coefficients (J values) in the upper atmosphere at both small and large solar zenith angles (SZA). In order to obtain the O₂ cross section between 49,000 and 57,000 cm⁻¹, an algorithm which considers the position, strength, and half width of each spectral line was used. Every transition was calculated by using the HIgh-resolution TRANsmission molecular absorption database (HITRAN) and a Voigt profile. The temperature dependence of both the strength and the half widths was considered within the range of temperatures characteristic of the US standard atmosphere, although the results show a very good agreement also at 79 K. The cross section calculation was carried out on a 0.5 cm⁻¹ grid and the contributions from all the lines lying at ±500 cm⁻¹ were considered for every wavelength. Both the SR and the Herzberg continuums were included. By coupling the LBL method to the TUV model, full radiative transfer calculations that compute J values including Rayleigh scattering at high altitudes and large SZA can now be done. Thus, the J values calculations were performed for altitudes from 0 to 120 km and for SZA up to 89°. The results show, in the J_O2 case, differences of more than ±10% (e.g. at 96 km and 30°) when compared against the last version of the TUV model (4.4), which uses the Koppers and Murtagh parameterization for the O₂ cross section. Consequently, the J values of species with cross sections overlapping the SR band region show variable differences at lower altitudes. Although many species have been analyzed, the results for only four of them (O₂, N₂O, HNO₃, CFC12) are presented. Due to the fact that the HNO₃ absorption cross section extends up to 350 nm this molecule was used to verify the consistency of the new TUV-LBL at lower altitudes. Thus, it shows differences up to 5.7% at 21 km but 0% in the troposphere. Because of the more accurate consideration of the Rayleigh scattering the distribution of the actinic flux in its direct and diffuse components (in the SR bands wavelength interval) is also modified.     

High-resolution FTIR spectrum of vinyl chloride: rovibrational analysis of the v 10 and v 11 fundamental bands

The Fourier transform gas-phase infrared spectra of the v ₁₀ and v ₁₁ bands of natural CH₂=CHCl have been measured with a resolution of 0.005 cm^?1 in the frequency range 820–1010 cm^?1. These vibrations of symmetry species A″ give rise to c-type bands and the transitions observed are characterized by δK _a = ±1 and δK _c = 0, ±2. Both J and K structures have been resolved in different subbranches and about 1800 (J ≤ 64, K _a ≤ 13) and 2800 (J ≤ 72, K _a ≤ 14) transitions for the v ₁₀ and v ₁₁ fundamentals, respectively, have been identified for the ³⁵Cl isotopomer. Combined analysis of the assigned data with the available ground state constants allowed the determination of the band origins, rotational and centrifugal distortion parameters for the v ₁₀ = 1 and v ₁₁ = 1 excited states of CH₂=CH³⁵Cl isotopic species. The molecular constants obtained account for slight perturbations in the v ₁₀ vibrational level.     

Neutron crystal-field spectroscopy and susceptibility in TmxY1−xAl2

Inelastic neutron scattering due to crystalline electric field transitions is observed in Tm_0.25Y_0.75Al₂. The best fit of the theoretical cross section to experiment is obtained for the Lea, Leask and Wolf parameters W = (0.040 ± 0.005)meV and X = (0.50 ± 0.05). The extrapolation of the measured susceptibility of Tm_xY_1?xAl₂(x = 0.05, 0.15, 0.25)tox = 0 is in good agreement with theory when using the above parameters.     

Experimental photoneutron cross sections of natural zirconium from 8 MeV to 134 MeV

The inclusive partial photoneutron cross sections and the total photoneutron cross section \(\sigma ^{(1)} (E_\gamma ) = \sum\limits_{i = 1}^{i_{\max } } {\sigma (\gamma ,in...)} \) for natural Zr have been measured from 8 MeV to 134 MeV, with monochromatic photons obtained by in flight annihilation of monoenergetic positrons. The integrated total photoneutron cross section up tillE _γ=140 MeV is (1.59±0.11)σ ₀, whereσ ₀ is the Thomas-Reiche-Kuhn sum-rule. The integrated total photonuclear absorption cross section is evaluated to be (1.73±0.15)σ ₀. The behaviour of the total photoneutron cross section as a function of Eγ, in the 40 MeV <E _γ<140 MeV energy range, is well described by a modified version of the quasideuteron model.     

Ro-vibrational spectra of C2H2 based on variational nuclear motion calculations

A published ab initio-based potential energy surface and newly constructed dipole moment surface of acetylene have been used to compute vibrational band intensities. The line intensity calculations employed the variational nuclear motion code WAVR4 for computation of wave functions and energy levels, and a newly developed code DIPOLE4 for computation of dipole transitions. Owing to the high computational cost of J > 0 transitions using direct variational methods only J = 0 and J = 1 states and transitions have been computed variationally. The intensities of J > 1 transitions were extrapolated from J = 0 and J = 1 using Hönl–London coefficients. The resulting effective rotational constants B and transition intensities are compared with experimental data for the (3ν₄ + ν₅) combination band, the ν₃ and the ν₅ fundamental band. The prospects of using this procedure for extensive calculations of a hot line list, important for cool stars and extrasolar planets are discussed.     

TheJ/Ψ absorption cross section in nuclei and color screening

Data on 120 GeV photoproduction ofJ/'s in nuclear targets are re-examined to extract the absorption cross section forJ/'s in high energy collisions with nucleons. We find _a =6.6±2.2 mb in contrast with an earlier estimate of 1–2 mb. Comparison of low and high energy data on photon producedJ/'s thus no longer show possible evidence for observable effects of color screening. Examination of representative data on the Feynmanx distributions ofJ/ production by hadrons demonstrates how to extract both the total inelasticJ/-nucleon cross section and the partial cross section into open charm. We find that the data is inconsistent with any significant contribution from color screening.     

Far infrared spectrum and spectroscopic constants of AsH3 in the ground state

The far ir spectrum of arsine, AsH₃, was recorded in the range 25–100 cm^?1 with a resolution of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0 rotational transitions were measured and assigned up to J″ = 12. These transitions, together with the presently available microwave and submillimeter-wave data and ground state combination differences, were analyzed on the basis of a rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The derived ground state molecular parameters reproduced the transition frequencies of both allowed and “perturbation allowed” transitions within the accuracy of the measurements. The equilibrium structure was determined for the AsH₃ molecule.     

Measurements of electron density, temperature and photoionization cross sections of the excited states of neon in a discharge plasma

In the present work emission and absorption spectroscopy have been used to determine the plasma parameters of neon in a hollow cathode discharge lamp. The excitation temperature is determined using the intensity ratio method and Boltzmann's plot method whereas the electron density is determined from the Stark broadening of the spectral lines. The behavior of the optogalvanic signal as a function of laser energy has been studied for three transitions from the 2p⁵3s [1/2]₂ metastable state following ΔJ=ΔK=0, ±1 dipole selection rules. The saturation technique has been used to measure the photoionization cross section from three intermediate states 2p⁵3p′ [1/2]_1, 2p⁵3p′ [3/2]₂ and 2p⁵3p [5/2]₃ up to the 2p^{5 2}P_1/2 ionization threshold.     

激发态铯原子间的碰撞能量转移

用激光抽运基态Cs₂分子,通过预离解或碰撞转移,由一部分的激发态Cs₂产生Cs原子6P,5D激发态。测量了Cs(5D)+Cs(6P)→Cs(7D_J)+Cs(6S)碰撞激发能量转移截面σ_(7DJ),以及Cs(7D_J)+Cs(6S)→除Cs(7D)外的态的截面σ_tr。结果是,对于J=5/2,3/2,σ_(7DJ)(以 关键词：