C3O2 as a semirigid bender: The degenerate ν5 state

The semirigid bender Hamiltonian for carbon su?ide C₃O₂ [P. R. Bunker, J. Mol. Spectrosc.80, 422–437 (1980)] is extended in a manner similar to the extension previously described for HCNO [P. Jensen, J. Mol. Spectrosc.101, 422–439 (1983)]. The extended Hamiltonian describes the manifold of large-amplitude vibrational states (due to the ν₇ CCC bending mode) superimposed on a high-frequency vibrational state involving excited quanta of the CCO bending modes ν₅ and ν₆. The extended model is used to fit CCC bending and rotation energy level separations for¹²C₃¹⁶O₂ superimposed on the ν₅ fundamental level. Due to the severely limited experimental data it is not possible to unambiguously determine the effective CCC bending potential energy function in the ν₅ state, but estimates of the potential energy parameters are obtained by determining them in two limiting cases.     

Selective effects of homogeneous and heterogeneous reactions in the system N21-CO

In the system N₂¹-CO, effects arising only from the reactions in the homogeneous phase have been isolated in a reactor with inert walls. After an induction period of 0.13 s, they involve a stationary rate of enhancement of N₂(B³Π_g) and N(⁴S) concentrations according to the reactions N₂(X¹Σ_g⁺)_v¹+CO→ CO(X¹Σ⁺)_v1 + N₂(X¹Σ_g⁺ and CO(X¹Σ⁺)_v1 + N₂(A³Σ_u⁺) → N (⁴S) + N(⁴S) + CO(X¹Σ⁺).In a reactor with active walls, both the above reactions in the homogeneous phase and heterogeneous reactions due to CO adsorbed on the walls are involved according to CO_ads + N₂(X¹Σ_g⁺)_{v1 ads or not} → CO(X¹Σ⁺)_v1 + N₂(X¹Σ_g⁺ and N(⁴S) + N(⁴S) + CO_ads → N₂(X¹Σ_g⁺) + CO(X¹Σ⁺)N(⁴S) + CO_ads → N₂(X¹Σ_g⁺) + CO(X¹Σ⁺). In this case, the rate of enhancement is not stationary. Furthermore, for cylindrical reactors with large diameters, the two types of reaction do not interact and their effects are additive.     

Analysis of Dissociation—Recombination Processes for the CO<Subscript>2</Subscript> Molecule with the Spin—Orbit Coupling Taken into Account

The dissociation CO₂(X¹Σ) + M → CO(X¹Σ) + O(³P) + M and recombination CO(X¹Σ) + O(³P) + M → CO₂(X¹Σ) + M processes are considered with the spin—orbit coupling taken into account in the ground and several excited states of the CO₂ molecule. Because of the specific features of mutual position of potential energy surfaces of the CO₂ molecule in the ground and several excited states and the large values of spin—orbit interaction matrix elements, which causes the quantum nonadiabatic transition of the molecule from one state to another, these processes become effectively spin-allowed and the rate constants for the nonadiabatic reactions have large values. The proposed dissociation and recombination mechanisms include reactions involving singlet—triplet crossings.     

Interaction of Zn atoms in the 1 S and 3 P states with N2 molecules in the X 1Σ g + and A 3Σ u + states at moderate distances between the atom and molecule

An asymptotic method was used to derive analytical expressions for the matrix elements of interaction between the N₂ molecule in the X ¹Σ _g ⁺ and A ³Σ _u ⁺ electronic states and the Zn atom in the ¹ S and ³ P states. Quadrupole-quadrupole, dispersion, and exchange interactions were taken into consideration. The character of the set of diabatic vibronic potential energy surfaces of the system suggests that the energy transfer in the process N₂(A ³Σ _u ⁺ ) + Zn(¹ S) → N₂(X ¹Σ _g ⁺ ) + Zn(³ P) may prove to be rather effective.     

Investigation of N 2 + (C 2Σ u + → X 2Σ g + fluorescence excited through auger decay of the 1s −1π* resonance

A theoretical investigation of N ₂ ⁺ (C ²Σ _u ⁺ → X ²Σ _g ⁺ molecular fluorescence excited through the Auger decay of the 1s ^?1π* resonance is carried out. The fluorescence cross sections are calculated with due regard for the dependence of the matrix element of the C → X dipole transition on the internuclear distance, the interference between channels of excitation via different vibrational levels v _r of the 1s ^?1π* resonance, the rotational structure of the fluorescence band, and the predissociation of the N ₂ ⁺ C ²Σ _u ⁺ v′ ≥3) states. The calculated cross sections are in good agreement with the experimental results of recent measurements. The results of the calculations have demonstrated that the observed dependence of the cross section of the (C ²Σ _u ⁺ (v′) → X ²Σ _g ⁺ (v″) fluorescence on the excitation energy and the fluorescence wavelength for a group of bands with equal values of the difference Δv = v′ ? v″ is associated with transitions between the vibrational levels of the electronic states involved in the excitation and subsequent cascade decay of the 1s ^?1π* resonance: N₂ (v ₀ = 0) → N*₂(1s ^?1π*(v _r)) ? N ₂ ⁺ : (C ²Σ _u ⁺ (v′) → X ²Σ _g ⁺ (v″).     

New limits for the exotic exchange reaction π−p → K+Σ− at 5 and 8 GeV

Measurement of the exotic exchange reaction π^?p → K⁺Σ^? has been performed at 5 and 8 GeV, in the ?0.015 to ?0.13 and ?0.009 to ?0.15 (GeV/c)² range of t repectively. We give the value near t = 0 of the differential cross section at 5 GeV, 21_?21⁺⁷⁶ nb/(GeV/c)², and an upper limit (< 37 nb/GeV/c)²) at 8 GeV. As a check the measured differential cross section is given at both energies for the reaction π⁺p → K⁺Σ⁺ in the same range of t.     

The Hg2 (A3Ou− → X1Σg+) and (A31u → X1Σg+) fluorescence

The fine structure emission sepctrum near 5500 Å attributed to the Hg₂ (A³O_u^? → X¹Σ_g⁺) transition is shown to be strikingly similar to the HgCl (B²Σ⁺ → X²Σ⁺) emission spectrum sensitized by Hg(6³P_o) metastables. The correct Hg₂ (A³O_u^? → X¹Σ_g⁺) emission spectrum at 4850 Å was re-examined and confirmed to be a continuous one. It is suggested that the fine structure arose from the sensitization of a chlorine containing impurity.     

Phase-shift analysis of π N → K Σ

We have performed an energy-independent phase-shift analysis of πN → KΣ by analyzing differential cross-section and polarization data for the reactions π⁺p → K⁺∑⁺ and

at fifteen energies from threshold to 2137 MeV invariant mass. The single-energy solutions were linked by shortest-path methods with and without constraints implied by the Odorico zeros for the reaction π^?p → K⁺Σ^?. Similar to π^?p → KΛ it has been found that both isostates are dominated below 1900 MeV by resonances in the spin $\text{1}\text{2}$ waves. The F₃₇ resonance couples to KΣ with √x_πNx_KΣ= 0.04.     

Vibrational analysis of the a3Σ+-X1Σ+ and b3Π-X1Σ+ band systems of GeS

Spectra of GeS have been obtained in a chemiluminescent flame produced by the reaction Ge + OCS → GeS + CO. Neither of the known band systems, D¹Π-X¹Σ⁺ and E¹Σ⁺-X¹Σ⁺, was observed, but two new band systems in the regions 350–400 and 420–650 nm were obtained. By comparison with similar systems in isovalent molecules, these were assigned as b³Π₁-X¹Σ⁺ and a³Σ⁺-X¹Σ⁺, respectively. Vibrational assignments were made with the help of the germanium isotope effect and vibrational constants were obtained for the states involved. Approximate Morse potential Franck-Condon factors were computed and were shown to fit the general trend of the intensity distribution for both systems. Addition of active nitrogen to the flame was shown to increase the intensity of the b-X system by an order of magnitude while hardly affecting the a-X system. Constants (in cm^?1) obtained for the two new states are: a³Σ⁺: T_e = 21986.3 ± 2.3, ω_e = 388.9 ± 1.0, ω_ex_e = 1.35 ± 0.11; b³Π₁: T_e = 27192.0 ± 1.8, ω_e = 435.4 ± 1.1, ω_ex_e = 1.68 ± 0.20.     

Electron-vibrational energy exchange in collisions of electronically excited N2(A 3Σ u + ) molecules with Zn(X 1 S) atoms

The interaction matrix between the N₂ molecule in the X ¹Σ _g ⁺ and A ³Σ _u ⁺ states and the Zn atom in the ¹ S and ³ P states calculated earlier by the asymptotic method was used to find the rate constants for the electron-vibrational energy exchange N₂(A ³Σ _u ⁺ , v) + Zn(¹ S) → N₂(X ¹Σ ₈ ⁺ , v′) + Zn(³ P). The calculations were performed by the transition state method, and the probabilities of transitions between intersecting electron-vibrational terms of the system in motion along the reaction coordinate were determined by the Landau-Zener equation. The calculated electron excitation transfer constants between N₂(A ³Σ _u ⁺ , v = 1, 0) and Zn(¹ S) over the temperature range 300–900 K were on the order of 10^?11?10^?12 cm³/s.     

Emission properties of an atmospheric-pressure helium plasma jet generated by a barrier discharge

The emission properties of an atmospheric-pressure helium plasma jet generated by a barrier discharge in a capillary blown with helium are studied. The spectral composition of the radiation of the studied plasma jet and the spatial-spectral distribution of its intensity are investigated in detail. It is shown that the emission spectrum of the generated plasma jet outside the capillary consists mainly of electronic-vibrational transitions of the first negative system of ionized nitrogen molecules N ₂ ⁺ (B ²Σ _u ⁺ → X ²Σ _g ⁺ ) and the second positive system of neutral nitrogen molecules N₂(C ³Π _u → B ³Π _g ).     

Ab initio nonadiabatic calculation of the sensitivity coefficients for the X 1Σ g + → B 1Σ u + ; C 1Πu lines of H2 to the proton-to-electron mass ratio

Ab initio nonadiabatic calculations of the wavelengths λ_ij of the individual lines of the Lyman X ¹Σ _g ⁺ → B ¹Σ _u ⁺ and Werner X ¹Σ _g ⁺ → C ¹Π_u series of molecular hydrogen and corresponding sensitivity coefficients K _ij = dlnλ_ij/dlnγ have been performed. These quantities are necessary for testing a possible change in the proton-to-electron mass ratio γ = m _p/m _e in the process of cosmological evolution. The basic contribution to K _ij comes from the difference between the average kinetic energies of vibrations of combined states. Nonadiabatic interactions are important for a small number of locally-perturbed rovibrational levels of the B ¹Σ _u ⁺ and C ¹Π _u ⁺ states, for which change in K _ij that is caused by nonadiabatic effects reaches 14%, which can lead to a significant systematic shift in the estimate of the parameter γ.     

Laser-induced fluorescence of GdO

A semiempirical calculation of the energy level diagram of GdO based on the ligand field theory is presented here. The main frame of the resulting scheme is very simple and should be useful in order to link together the numerous observed systems of GdO. Pulsed dye laser-induced fluorescence experiments made possible the evaluation of some of the ligand field theory predictions, particularly that a Y⁷Σ⁻ level is lying 1840 cm⁻¹ above the X⁹Σ⁻ ground state. The I and II systems are shown to arise from the B⁹Σ⁻-X⁹Σ⁻ and B₁⁷Σ⁻-Y⁷Σ⁻ transitions, respectively. Continous wave laser-excitation spectra have been recorded and rotational analysis of the A⁹Π₄ → X⁹Σ⁻ transition carried out, confirming previous results of N. N. Dmitriev, L. A. Kaledin, E. A. Shenyavkaya, and L. V. Gurvich (Acta Phys. Hung. 55, 467–479 (1984)).     

Ab initio studies of electronic spectra of the linear aluminum-bearing carbon chains AlC2nH (n = 1-5)

Geometries and stabilities of the linear aluminum-bearing carbon chains AlC_2nH (n = 1-5) in their ground states have been explored by the DFT-B3LYP and RCCSD(T) methods. Structures of the X¹Σ⁺ and 1¹Π electronic states have also been optimized by the CASSCF approach. The studies indicate that these species have single-triple bond alternate pattern, AlCCCC?CCH, and the electronic excitation from X¹Σ⁺ to 1¹Π leads to the shortening of the AlC bonds. The vertical excitation energies of the 1¹Π ← X¹Σ⁺ and 2¹Π ← X¹Σ⁺ transitions for AlC_2nH (n = 1-5) have been investigated by the CASPT2, EOM-CCSD, and TD-B3LYP levels of theory with the cc-pVTZ basis set, respectively. CASPT2-predicted 1¹Π ← X¹Σ⁺ transition energies are 3.57, 3.44, 3.33, 3.26, and 3.21 eV, respectively. For AlC₂H, our estimate agrees very well with the experimental value of 3.57 eV. In addition, the AlC bond dissociation energies and the exponential-decay curves for these vertical excitation energies are also discussed.     

Mixed state ultrasonic attenuation in clean niobium near Hc2

Both longitudinal and shear ultrasonic attenuations and magnetization were measured as a function of magnetic field in the mixed state of two niobium single crystal samples with residual resistivity ratios of 68 and 2665 respectively. Particular attention was paid to the behavior of the attenuation at fields near H_c2. The higher purity sample showed marked frequency dependence of normalized attenuation at frequencies from 10 to 110 MHz. The other sample showed qualitatively similar but less pronounced frequency dependence at frequencies ranging from 10 to 435 MHz. Frequency dependence in both samples was in qualitative agreement with the theoretical results of Cerdeira and Houghton[1]. The attenuation changes near H_c2 at the lowest experimental frequencies were compared quantitatively with the frequency independent theoretical results of Houghton and Maki[2]. Agreement in the less pure sample was within a factor of two of the Houghton-Maki results at both 4·2 and 1·4 K. Quantitative comparison to theory for the purer sample must be qualified by the large observed frequency dependence. However, agreement between theory and experiment was excellent at 4·2 K. At 1·4 K in the purer sample, the theoretical predictions differed from experimental results by factors from two to six for various configurations of magnetic field and ultrasonic propagation and polarization directions. Houghton-Maki predictions of the dependence of ultrasonic attenuation on the geometry of magnetic field and ultrasonic propagation and polarization direction were also examined.     

Chemiluminescence of bromine vapor under pulsed lamp pumping

The chemiluminescence kinetics and spectrum of gaseous Br₂ under the conditions of broadband optical pumping have been investigated. It has been found that the transition A ³Π_1u → X ¹Σ _g ⁺ is the major contributor to the luminescence spectrum.     

Comparison of photoelectron intensities and Franck-Condon factors in the photoionization of H2, HD and D2

The relative intensities of vibrational bands corresponding to the photoionization reactionX¹Σ_g⁺(υ″ = 0) + hv → X²Σ_g⁺(υ′ = 0, 1, 2 …) + e^? have been measured for H₂, HD and D₂, using He I radiation and a cylindrical mirror analyzer. These relative intensities differ significantly from squared overlap integrals (Franck-Condon factors) based on accurate potential curves for X¹Σ_g⁺ and X²Σ_g⁺, but are in good agreement with calculations performed by Itikawa which include the variation of transition moment with internuclear distance and the kinetic energy of the departing electron.     

Franck-Condon factors and r-centroids for the RKRV potential (A2IIr → X2Σ+ transition of BeCl)

Turning points of the vibrating BeCl molecule in the A²II_r and X²Σ⁺ electronic states are evaluated using the RKRV potential. The Franck-Condon factors and r-centroids have been computed for the A²II_r → X²Σ⁺ transition using wave functions appropriate to the RKRV potential curve. The results are consistent with the intensity distribution in the vibrational bands for the specified transition. The sequence difference Δ$\text{r}$ remains approximately constant for the r-centroids.     

First observation of the production and decay of the Σc+

An event with the decay chain Σ_c⁺ → Λ_c⁺ + π⁰, Λ_c⁺ → K^? + p + π⁺, has been observed in an exposure of BEBC, equipped with a track sensitive target, to the wide band neutrino beam from the SPS at CERN. The event has a unique three constraint kinematic fit to the ΔS = ?ΔQ reaction v + p → μ^? + p + K^? + π⁺ + π⁺ + π⁰ with both gammas from the π⁰ decay detected. The proton and other final state particles are identified. The masses are M(Λ_c⁺) = 2290 ± 3 MeV/c², M(Σ_c⁺) = 2457 ± 4 MeV/c² and M(Σ_c⁺) ? M(Λ_c⁺) = 168 ± 3 MeV/c². Including other data one obtains M (Σ_c⁺⁺) ? M(Σ_c⁺) = 0 ± 4 MeV/c².     

The B2Σ+-X2Σ+ system of Sr79Br and Sr81Br: Rotational and vibrational analyses

Doppler-free laser polarization spectroscopy has been used to record the (0, 0), (1, 1), and (2, 2) bands of the B²Σ⁺-X²Σ⁺ system for both Sr⁷⁹Br and Sr⁸¹Br. With the help of microwave labeling and additional band selective detection of the laser-induced fluorescence a rotational analysis could be performed. The optical data were combined with the results of independent microwave measurements of the X²Σ⁺ state in a weighted least-squares fit. Local perturbations were observed in each vibrational state of B²Σ⁺. Bandhead positions of Δv = ±1 bands were used for the vibrational analysis.