Oscillator strengths from line absorption in a high-temperature furnace—II. The (0,0) band of the B2σ+—X2σ+ transition in CN*

Quantitative high-resolution absorption spectroscopy was applied to the (0,0) violet band of CN. The CN radical was prepared in a furnace at 1421°K containing pure cyanogen gas. Since the calculated CN concentration is dependent on the controversial CN heat of formation, only the relationship, f_υ = 6·84 X 10^-3exp (0·354δ), where f_υ is the excess over the initially assumed ΔH⁰_f(CN) = 100·8 kcal/mole, could be directly determined in this study with an estimated error in f_υ of ±20%. For δ = 0, our f_υ is a factor of 4·8 smaller than an average value of 0·033±0· derived from other measurements. If this latter value of f_υ is assumed, our relationship yields ΔH⁰_f(CN) = 105·3±1· kcal/mole or D₀(CN) = 7·66±0·05 eV. The rotational temperature and line widths for this band were also measured.     

A potential hydroxyl ultraviolet laser

A strong emission band extending from 3060 to 3120 Å was observed following proton beam excitation of an Ar-H₂O mixture. This emission band was assigned to the transition of OH(A²Σ⁺)_υ=0 → OH(X²Π)_υ=0. At high argon partial pressure (> 200 torr), the precursor of this emission band is believed to be the argon excimer Ar^★₂(1_u). The fluorescence efficiency of Ar-H₂O is estimated to be a factor of 4 times that of Ar-N₂. Development of a highly efficient, tunable uv laser by e-beam pumping is promising.     

Deexcitation of Cd 53P1 atoms in collisions with ground state atoms and molecules

Collisions of excited Cd 5³P₁ atoms were investigated using atomic fluorescence spectroscopy. Cadmium vapor, together with a quenching gas, was irradiated in a quartz fluorescence vessel with Cd 3261 Å resonance radiation and the intensity of the resulting resonance fluorescence was monitored in relation to the gas pressures. The experiments yielded the following cross sections Q₁₀ (in A²) for collisional transfer 5³P₁→5³P₀: CdAr=2×10^?3, CdN₂=8.0, CdH₂=7.0, CdCO=15.6. The cross sections Q for collisional deexcitation to the ground state (quenching) in A² are CdN₂ = 2.6×10^?2, CdH₂ = 11.0, CdCO = 3.4, CdCO₂ = 26.     

Photoionization and photoelectron angular distribution for H2

Photoionization of H₂(¹Σ_g⁺) in a vibrational υ″ and rotational N″ state into H₂⁺(²Σ_g⁺) in a vibrational υ′ and rotational N′ state is studied theoretically. The differential cross section, after summing over the final states, is expressed in the well-known simple form of $\text{(}\text{σ}{}_{\mathrm{T}}\text{4π}\text{)[1 + βP}{}_2\text{(}\text{cos}\text{θ)]}$. Parallel expressions are obtained for H₂⁺ in a specific υ′ state (in terms of σ(υ′) and β(υ′)) and for H₂⁺ in a rotational fine level υ′N′ (in terms of σ(υ′N′) and β(υ′N′)). Asymmetry parameters β, β(υ′) and β υ′N′), which are expressed in terms of Racah and Clebsch-Gordan coefficients and electronic transition moments, can be reduced approximately to 2 lineary polarized light and to -1 for unpolarized light. Using single-center electronic wave functions and including partial eaves l = 1, 3, and 5, σ(υ′) and β(υ′) are computed as a function of υ′ at 584 Å. The computed σ(υ′) divided by the Frank-Condon overlap, in agreement with experimental results, increases monotonically with υ′; σ_T and β are computed in the incident photon energy range of 600–4000 Å and the results compare favorably with previous calculations.     

Radiative lifetimes and electronic quenching rate constants for single-photon-excited rotational levels of no (A2Σ+, ν′ = 0)

A narrow-band, frequency-doubled, tunable dye laser has been used to excite fluorescence from the A²Σ⁺, ν′ = 0 state of NO. Collision-free lifetimes were measured for 21 different K′ levels giving a mean radiative lifetime τ = 217 ± 4 ns. Electronic quenching rate constants of NO (A²Σ⁺, ν′ = 0) were measured for O₂, N₂, H₂O, CO₂ and Ar. No dependence of the quenching-rate constant on the initially excited rotational level was observed.     

Doppler-free high resolution spectroscopy of carbon disulphide and the effects of a magnetic field

A single-mode autoscan laser spectrometer operating in the ultraviolet in combination with a collimated molecular beam was used to measure high resolution fluorescence excitation spectra of the CS₂ V ¹B₂ ← X ¹Σ⁺ _g transition under collision-free conditions, and the effects of a magnetic field were measured. Rotational and vibrational levels were fully resolved, and Zeeman splittings were observed in many of the perturbed lines. The Zeeman interaction was observed to induce new perturbation, which induces new transitions, level splitting, and energy shift. When the magnetic field strength was changed, the magnitude of the interaction, which was observed in the absence of a magnetic field, changed dramatically depending on the energy shifts of the Zeeman components. It is shown that the V ¹B₂(¹Δ_u) state is mixed with the B₂(³A₂) component by first-order spin-orbit interaction, and through the mixed component, the Zeeman interaction between the V ¹B₂(¹Δ_u) and ³A₂(³Δ_u) states is induced. Large Zeeman splittings were observed for most of the background lines of weak intensity, and this demonstrates that the background levels are levels of the ³A₂(³Δ_u) state. The fluorescence decays of single Zeeman components were observed to be single exponential. The lifetimes of the perturbing ³A₂(³Δ_u) levels were determined by deperturbation analysis. Triplet-triplet ³A₂(³Δ_u) → ³B₂(³Σ⁺ _u) emission was confirmed. It was demonstrated that the quenching of the V ¹B₂ → X ¹Σ⁺ _g fluorescence by a magnetic field was caused by mixing of the ³A₂ state with the V ¹B₂ state and the resulting increase of triplet-triplet emission. In a time-dependent picture, the intersystem crossing from the ¹B₂(¹Δ_u) and ³A₂(³Δ_u) states is enhanced by the magnetic field.     

An intermodulated fluorescence study of the A2Σ−-X2Πi band system of copper monoxide

Several lines in the A²Σ⁻(v = 0)-X²Π_i(v = 0) visible band system of gas phase copper monoxide have been measured at sub-Doppler resolution using the technique of intermodulated fluorescence. The copper nuclear magnetic hyperfine splitting is clearly resolved. The observations were fitted to an effective Hamiltonian model and values of the magnetic hyperfine parameters of b_F = −0.0302 cm⁻¹ for the A state and d = 0.0024 cm⁻¹ for the X state were determined. An interpretation of these values in terms of the proposed electronic configurations of these states is presented.     

1+ state and effective g-factor

The effects of nuclear field r²(Y₂σ₁)_1υ on magnetic properties of single-particle states in odd-A nuclei (^208±1Pb) are considered. The coupling constant associated with this type of field is estimated by an argument that realtes it to the coupling constant for the field (γ₀σ₁)_1υ. The effects of including the r²(Y₂σ₁)_1υ field on the M1 moments and transitions are estimated.     

Dimeric Fe (II, III) complex of quinoneoxime as functional model of PAP enzyme: Mössbauer, magneto-structural and DNA cleavage studies

Purple acid phosphatase, (PAP), is known to contain dinuclear Fe₂ ^?+?2,?+?3 site with characteristic Fe^?+?3 ← Tyr ligand to metal charge transfer in coordination. Phthiocoloxime (3-methyl-2-hydroxy-1,4-naphthoquinone-1-oxime) ligand L, mimics (His/Tyr) ligation with controlled and unique charge transfers resulting in valence tautomeric coordination with mixed valent diiron site in model compound Fe-1: [μ-OH-Fe₂ ^?+?2,?+?3 (o-NQ_CH3ox) (o-NSQ_CH3ox)₂ (CAT) H₂O]. Fe-2: [Fe^?+?3(o-NQ_CH3ox) (p-NQ_CH3ox)₂]₂ a molecularly associated dimer of phthiocoloxime synthesized for comparison of charge transfer. ⁵⁷Fe Mössbauer studies was used to quantitize unusual valences due to ligand in dimeric Fe-1 and Fe-2 complexes which are supported by EPR and SQUID studies. ⁵⁷Fe Mössbauer spectra for Fe-1 at 300 K indicates the presence of two quadrupole split asymmetric doublets due to the differences in local coordination geometries of [Fe^?+?3]_A and [Fe^?+?2]_B sites. The hyperfine interaction parameters are δ _A = 0.152, (ΔE _Q)_A = 0.598 mm/s with overlapping doublet at δ _B = 0.410 and (ΔE _Q)_B = 0.468 mm/s. Due to molecular association tendency of ligand, dimer Fe-2 possesses 100% Fe^?+?3(h.s.) hexacoordinated configuration with isomer shift δ = 0.408 mm/s. Slightly distorted octahedral symmetry created by NQ_CH3ox ligand surrounding Fe^?+?3(h.s.) state generates small field gradient indicated by quadrupole split ΔE _Q = 0.213 mm/s. Decrease of isomer shifts together with variation of quadrupole splits with temperature in Fe-1 dimer compared to Fe-2 is result of charge transfers in [Fe₂ ^?+?2,?+?3 SQ] complexes. EPR spectrum of Fe-1 shows two strong signals at g ₁ = 4.17 and g ₂ = 2.01 indicative of S = 3/2 spin state with an intermediate spin of Fe^?+?3(h.s.) configuration. SQUID data of $\chi _m^{{\rm corr}} \mbox{.T}$ were best fitted by using HDVV spin pair model S = 2, 3/2 resulting in antiferromagnetic exchange (J = ?13.5 cm^???1 with an agreement factor of R = 1.89 × 10^???5). The lower J value of antiferromagnetic exchange leads to Fe⁺³μ-(OH) Fe^?+?2 bridging in Fe-1 dimer instead of μ-oxo bridge. The intermolecular association through H-bonds may lead to weakly coupled antiferromagnetic interaction between two Fe-2 molecules having Fe^?+?3(h.s.) centers. Using S = 5/2, 5/2 spin pair model we obtained best-fitted parameters such as J = ?12.4 cm^???1, g = 2.3 with R = 3.58 × 10^???5. Synthetic strategy results in non-equivalent iron sites in Fe-1 dimer analogues to PAP enzyme hence its reconstitution results in pUC-19 DNA cleavage activity, as physiological functionality of APase. It is compared with nuclease activity of Fe-2 RAPase.     

Pulsed supersonic source of vdW complexes for high-temperature applications: Spectroscopy and beam characteristics

Application of a modified version of high-temperature high-pressure all-metal pulsed source of supersonic molecular beam is demonstrated in a production of van der Waals (vdW) complexes. The vdW complexes are produced possessing controllable rotational temperature (T _rot ) in the range from 3 K to 19 K. An effective control over T _rot is illustrated employing excitation spectrum recorded using the B ³1(5³ P ₁) ← X ¹0⁺(5¹ S ₀) transition in CdAr. First-time resolved rotational structure in the profile of the υ′ = 2←υ′′ = 0 vibrational component is reported. The control over T _rot is crucial in a dissociation of the (¹¹¹Cd)₂ isotopologue in the supersonic beam. For the process, excitation at well defined J′← J′′ rotational transition within the (υ′,υ′′) = (40,0) vibrational band of the A ¹0 _u ⁺(5¹ P ₁) ← X ¹0 _g ⁺(5¹ S ₀) transition is employed. It is followed by the dissociation using A ¹0 _u ⁺(υ′ = 40,J′′) → X ¹0 _g ⁺ bound → free transition. An analysis and simulation of the (40,0) vibrational band rotational structure are presented. Parameters describing conditions in the supersonic beam, degree of rotational cooling, Doppler broadening and spectral bandwidth of the laser beam are used.     

High-Resolution Survey of the Visible Spectrum of NiF by Fourier Transform Spectroscopy

High-resolution spectra of NiF have been recorded in emission by Fourier transform spectroscopy using a very stable discharge source. The 0-0 bands of 14 electronic transitions have been studied, 6 of them for the first time. This work confirms the presence of 5 low-lying spin components X²Π_3/2, [0.25]²Σ⁺, [0.83]A²Δ_5/2, [1.5]B²Σ⁺, and [2.2]A²Δ_3/2 as known from previous laser-induced fluorescence experiments. Eight electronic states are now identified in the 18 000-24 000 cm⁻¹ range above the ground X²Π_3/2 state. Electronic assignments for these excited states are not always obvious because of violations of the selection rules and unusual fine structure parameters. We think that some of the upper states are spin components of quartet states. In such a congested spectrum, high-resolution spectra are best analyzed in conjunction with an energy level diagram constructed mainly by dispersed low resolution laser-induced fluorescence.     

Infrared transitions of C2D6 from v 4 to the interacting system v 4+ v 6, v 4+ v8, v 3+ 2v 4: rotational analysis,and torsional splitting in the v 3+ 2v 4 and v 3+ v 4 states

The hot infrared transitions of C₂D₆ from the υ₄(A_1u ) to the υ₄ + υ₆(A_2g ) and υ₄ + υ₈(E _g ) vibrational states, observed from 960 to 1180 cm^?1, have been rotationally analysed on a high-resolution Fourier transform spectrum (full width at half-maximum about 0·0030 cm^?1). The vibration-rotation interactions affecting the upper vibrational states are very similar to those of the corresponding cold system. A strong x,y Coriolis interaction between υ₄ + υ₆ and υ₄ + υ₈, with K-level crossing, generates large displacements of the rotational components of both vibrational states, tuning them to additional local resonances in several spectral regions. Thus l resonances with Δl = ±2, Δk = ±1 occur within υ₄ + υ₈. A x,y Coriolis-type resonance between υ₄ + υ₈(?l,K ? 1) and υ₃ + 2υ₄(K) occurs at K = 11,12,13, and a further coupling of υ₄ + υ₈(+l,K + 1) and υ₃ + 2υ₄(K + 3) is most effective at K = 11 and 12. These resonances induce torsional splittings on the perturbed levels of υ₄ + υ₈ and allow us to determine the torsional splittings in the υ₃ + 2υ₄ state. The vibration-rotation constants of υ₄ + υ₆, υ₄ + υ₈ and υ₃ + 2υ₄, several interaction parameters and the torsional splitting of υ₃ + 2υ₄ have been determined by least-squares fit of 1391 observed transition wavenumbers, with an overall standard deviation σ = 0·75 × 10^?3 cm^?1. The vibrational wavenumbers found for the four torsional components of (υ₃ + 2υ₄)? υ₄ are υ(E_3d) = 1040·961 82(809)cm^?1, υ(A_3d) = 1041·218 27(865)cm^?1, υ(E_3s) = 1041·225 23(662)cm^?1 and υ(A_1s) = 1041·407 77(633)cm^?1. These are anomalous for both the order of the torsional components and the magnitudes of their separations. We believe that this is mainly due to the interactions of υ₃ + 2υ₄ with the torsional manifolds with υ₃ = 0 and υ₃ = 2, through the vibration-torsion Hamiltonian term (?V ₆/?q ₃)q ₃cos (6γ)]/2. The further observation of a few doublets of υ₈ and υ₃ + υ₄ at resonance provides information on the torsional splitting of the latter state.     

L ∞ estimates for the space-homogeneous Boltzmann equation

This paper studies the boundedness of solutionsf of the initial-value problem for the space-homogeneous Boltzmann equation for inverse kth power forces, whenk>5, and under angular cutoff. The main result is that if the initial value isf ₀ ? 0 with (1 + ¦υ¦²)φ₀ εL ¹ and (1 + ¦υ¦)^s f ₀ε L^∞ for somes > 2, then (1 + ¦υ¦^s'f _tεL ^∞ fort>0 and ess_υ,t sup(1 + ¦υ¦)^s'f(υ, t,) < ∞ for anys′ ? s whens ? 5, and anys′ ? s ifs > 5.     

Flame spectroscopy of TiO: Photoluminescence of the α(C3Δ-X3Δ) system

Laser-induced photoluminescence has been observed from TiO molecules produced in a chemiluminescent flame. Using Ar⁺ and cw dye lasers, a detailed study has been made of photoluminescence of the α(C³Δ-X³Δ) system. Techniques are developed for assigning photoluminescence transitions involving states of high multiplicity in molecules with several isotopes. Assignment of a new C³Δ₃-a¹Δ transition places the a¹Δ state at 3444 ± 10 cm^?1 above the X³Δ state. Photoluminescence of the 0-0 band of the β(c¹Φ-a¹Δ) system, observed with 476.5 nm excitation, is shown to result from collisional relaxation of the C³Δ (v = 2) to c¹Φ (v = 0) states.     

Oscillator strengths for SiH and SiH deduced from the solar spectrum

Recent identifications of SiH (A²Δ-X²Π) and SiH⁺ (A¹Π-X¹Σ⁺) in the solar photospheric spectrum have enabled us to derive absolute oscillator strengths for the (0, 0) bands of these transitions: f₀₀(SiH) = 0.0033 and f₀₀(SiH⁺) = 0.0005. Our result for SiH is compared with other values.     

EPR of Mn2+ doping unannealed single crystal of (La2O3)0.95(CeO2)0.05

X-band room temperature EPR spectra have been recorded for Mn²⁺ ion doping unannealed (La₂O₃)_0.95(CeO₂)_0.05 host crystal. The data are analysed using a rigorous least-squares fitting procedure in which a large number of lines characterized by ΔM = ± 1, Δm = 0 transition, obtained for several orientations of the static magnetic field, are simultaneously fitted. Combined with the knowledge of the absolute sign of the hyperfine interaction parameter. A, the hyperfine Hamiltonian parameters A, B, Q as reported in this paper, are given with their correct signs. The information on the linewidth is used to deduce the deviation of the crystal-field axes of different Mn²⁺ ions from the c axis; on the basis of the model proposed here these deviations are found to be between 0 and 10°.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

Polarization spectroscopy of ICl: The D′, a and a′ states

Three previously-unanalyzed states of ICl are reported, an ion-pair state D′(Ω =2) which converges to the limit I⁺(P₂+ Cl^-(S_o), and two shallow states a(Ω = 1) and a′(Ω = 0⁺) both of which converge to the ground states of separated atoms I(P_{$\text{3}\text{2}$}) + Cl(P_{$\text{3}\text{2}$}). The a(0⁺) state is responsible for the well-known interruption of the B(0⁺) state above υ_B = 3. Spectroscopic constants are given for the D′ and a′ states.     

Hyperfine structure investigations in the4F9/2 atomic ground state of191Ir and193Ir

The5d ⁷6s^{2 4}F_9/2 atomic ground state of¹⁹¹Ir and¹⁹³Ir has been studied using the atomic-beam magnetic-resonance method. The results are:¹⁹³Ir:g _J(⁴F_9/2)=1.29694 (3)¹⁹¹Ir:Δv(⁴F_9/2; F=6?F=5)=659.26496 (12) MHzΔv( ⁴F_9/2; F=5?F=4)=189.44002 (09) MHzΔv( ⁴F_9/2; F=3?F=4)=84.05040 (80) MHzA=57.52148 (04) MHzB=471.20425 (57) MHzC=?0.020 (30) kHz¹⁹³Ir:Δv( ⁴F_9/2; F=6?F=5)=660.09043 (12) MHzΔv( ⁴F_9/2; F=5?F=4)=224.47848 (13) MHzΔv( ⁴F_9/2; F=?F=4)=33.53453 (89) MHzA=62.65556 (05) MHzB=426.23546 (64) MHzC=0.020 (30) kHz Using the magnetic dipole moments known by NMR-technique [1] we obtained for the electric quadrupole moments as calculated from the hyperfine interaction constantsA andB:Q(¹⁹¹Ir)=0.78 (20) barns,Q(¹⁹³Ir)=0.70 (18) barns (uncorrected for core polarization effects). A calculation of the hyperfine anomaly yields:₁₉₁ Δ ₁₉₃=?0.00023 (10). The ratio of theB factors which should be the same as for the quadrupole moments turned out to be:B(¹⁹¹Ir)/B(¹⁹³Ir)=Q(¹⁹¹Ir)/Q(¹⁹³Ir)=1.105502(3).