Radiative lifetimes of the Rb(n 2 F)(n=6, 7, 8) states measured with the stepwise dipole-quadrupole excitation scheme

We report measurements of lifetimes of the Rb(n ² F)(n=6, 7, 8) states performed in a vapour cell. TheF-states were excited in a two-step sequence of an electric-dipole transition followed by an electric-quadrupole transition. Single photon counting was used for detection. The results are: (6² F)=171(4), (7² F)=262(15), (8² F)=387(12) (in ns). These lifetimes, have been compared with theoretical values given by different authors. An estimate of the cross sections for quenching due to collisions with ground-state Rb atoms is also given.This work was supported by the Polish Committee for Scientific Research under grant No. 2 2341 92 03     

Radiative lifetime determination for the 3s4p-1P1 state of magnesium using pulsed level-crossing spectroscopy

The natural radiative lifetime of the 3s4p ¹ P ₁ level of neutral magnesium was measured by pulsed level-crossing spectroscopy at the short excitation wavelength of 202.6 nm. We obtained =13.4(5) ns for this state, strongly deviating from a previous beam-foil result, but in good agreement with a multi-configuration Hartree-Fock calculation. A discussion of the applicability of the pulsed Hanle effect method is given.     

Lifetime measurements of the 2p 3d 3 D 1, 2, 3 0 and 2p 3d 1 P 1 0 levels in NII by beam-foil-laser spectroscopy

Accurate lifetimes measured by means of the cascade-free method based on laser excitation of a fast ion beam preexcited in a carbon foil are reported for four 2p 3d levels in NII. The lifetime results are: τ(2p 3d ³ D ₁ ⁰ )=0.209±0.007 ns, τ(2p 3d ³ D ₂ ⁰ )=0.219±0.007 ns, τ(2p 3d ³ D ₃ ⁰ )=0.217±0.005 ns, and τ(2p 3d ¹ P ₁ ⁰ )=0.410±0.017 ns. These results are compared to theoretical and experimental lifetimes reported previously.     

Lifetime measurements of the 3D3/2 and 3D5/2 metastable states in CaII

The lifetime of the metastable 3D_3/2 and 3D_5/2 states of Ca⁺ ions is determined in a r.f. ion trap by laser excitation of this levels and subsequent time delayed probing of the state population by a second laser. In a buffer gas atmosphere of about 10^–5–10^–6 mbar of He we observe quenching to the ground state and strong finestructure mixing of the two D-states. This mixing allowes only the determination of the combined lifetime. Our result of (3D)=1.24(39) s is in good agreement with theoretical calculations.     

Lifetimes of the 4s4p 3 P 1 and 4s3d 1 D 2 states of Ca I

The lifetimes of the 4s4p ³ P ₁ and 4s3d ¹ D ₂ metastable states of Ca have been studied using the time-of-flight technique. Two kinds of observations were performed. First, the exponential decay of the fluorescence, using a (continuous) dc discharge for excitation and then the velocity distribution of the radiating atoms, using a pulsed discharge, were measured. From the combined results of these measurements the lifetimes were derived. The lifetimes of the 4s4p ³ P ₁ and 4s3d ¹ D ₂ states of Ca are determined to be 0.57±0.03 ms and 1.5±0.4 ms, respectively.     

The spin-allowed and spin-forbidden 5s 2 1 S 0-5s5p 1 P 1,3 P 1 transitions in strontium isoelectronic sequence

Relativistic multiconfiguration Dirac-Fock (MCDF) transition energies and oscillator strengths are determined for both the spin-allowed 5s ^{2 1} S ₀-5s5p ¹ P ₁ and the spin-forbidden 5s ^{2 1} S ₀-5s5p ³ P ₁ transitions in the strontium isoelectronic sequence. The modest relativistic configuration mixing to represent intravalence correlation is combined with a polarization model to account for valence-core electron correlations. The multiconfiguration Dirac-Fock calculations are performed in an average level scheme; however for neutral strontium and singly ionized yttrium a thorough comparison of the average and the optimal level schemes is presented. The average level scheme, though less accurate for the neutral end of the sequence, avoids the convergence problems encountered for highly ionized systems, where the 5s 5p ³ P ₁,¹ P ₁ states are raised owing to the collapse of the 4d _{3/2, 5/2} spin-orbitals in the isoelectronic sequence and, thus, allows us to extend our study to multiple charged ions (throughW ³⁶⁺). Since for such systems there is practically no difference between the results of the average and the optimal level versions of MCDF calculations, we believe that our average level predictions of ionization energies and oscillator strengths for states with total angular numberJ=0 andJ=1 are of comparable quality to those that could be obtained with an optimal level scheme.This study was supported by the Pedagogical Academy of Kraków Statutory Activity Grant No BS-29/91     

Radiative lifetimes of the 6p 2 P 1 2/0 and 6p 2 P 3 2/0 levels in Yb II

Radiative lifetimes have been determined for the 6² P ₁ ^2/0 and 6² P ₃ ^2/0 levels in Yb II using the method of laser-induced fluorescence from sputtered metal vapour. The results, 8.0(2)ns (6² P ₁ ^2/0 ) and 6.3(3)ns (6² P ₃ ^2/0 ), are compared with lifetimes obtained from ab initio manybody perturbation calculations.     

CPS GL 799

The effect of illumination on transport of sulfonated bisazo direct dyes, CI Direct Yellow 12, and CI Direct Yellow 4, into a cellulose membrane has been studied at various temperatures. Transport of CI Direct Yellow 12, which exhibits photoinduced reversible trans-cis isomerism in aqueous solution into a cellulose membrane, was influenced by illumination. It is likely that the transport was influenced by transisomerization of the photoisomeric dye and the diffusivity was controlled by surface diffusion rather than by pore diffusion under both light and dark conditions.Notations C Concentration of dye in the pores (mol/dm³) - C _E Concentration of electrolyte in the bulk solution (mol/dm³) - C _o Concentration of dye in the bulk solution (mol/dm³) - D _p Pore diffusivity (m²/s) - D _s Surface diffusivity (m²/s) - [M] Mean concentration of dye in membrane (mol/dm³) - [M] _L Local concentration of dye in membrane (=q+ _p C) (mol/dm³) - [M] Mean concentration of dye in membrane (mol/kg) - [M] _L Local concentration of dye in membrane (=q/V+ _p C) (mol/dm³) - F Fractional attainment of equilibrium - l Thickness of membrane (m) - q Concentration of dye adsorbed on pore wall (mol/dm³) - q _o Adsorbed concentration of dye in equilibrium withC _o (mol/dm³) - q Concentration of dye adsorbed on pore wall (mol/kg) - q _o Adsorbed concentration of dye in equilibrium withC _o (mol/kg) - t Time (s) - V Volume of membrane swollen with water per unit dry cellulose (dm³/kg) - x C/C _o - y q/q _o - z Distance that the dye diffused in the membrane (m) - q _o / _o C _o - D _s /D _p - Coefficient of the Freundlich isotherm - _p Pore void fraction - z/l - _p D _p t/l ² - _s D _s t/l ²     

Positron annihilation in polyvinylalcohol doped with CuCl2

Positron annihilation lifetime spectra were measured forpolyvinylalcohol (PVA) doped with CuCl₂ (0.5 to 5.0 wt%) at temperature range from room temperature to 160°C. For a fresh pure PVA (without annealing) ₃ belowT _g was larger in the heating runs than in the cooling runs, but aboveT _g, ₃ was the same for both runs. The larger ₃ values in the heating run were considered to be due to the existence of strain brought forth in the process of preparation. For annealed pure PVA ₃ was the same for the heating and the cooling runs andT _g was shifted to lower temperature, 88 and 80°C for fresh and annealed samples, respectively. This shift was attributed to loss of H-bonded water in the annealed pure PVA by heating above 100°C. BothI ₃ ⁰ and ₃ were decreased by the added CuCl₂, being interpreted as the result of inhibition and quenching, respectively. The results show that both the inhibition coefficient and the quenching rate constantk were smaller than the corresponding values in liquids. The small diffusion constant ofo-Ps estimated fromk implies thato-Ps is not very mobile in the polymer.     

A positron lifetime and Doppler-broadening study of positron states and free volume in polyethylene

Positron lifetime (LT) and Doppler-broadening (DB) studies of polyethylene have been performed simultaneously in the temperature range between 80 and 300 K. The LT spectra have been analysed assuming four exponential components. Two long-lived components appear, which were attributed too-Ps pick-off annihilation in crystalline regions (₃ = 0.9 to 1.2 ns) and at free-volume holes in the amorphous phase ( to 2.8), The variation in ₄ correponds to an increase of the mean hole size from 0.053 nm³ at 80 K to 0.188 nm³ at 300 K. From the data the glass transition temperature (T _g=195 K), the coefficient of thermal expansion of holes in the glassy and rubbery phase ( _{h, g} = 14.5 · 10^–4 K^–1 and _{h, r} = 189 · 10^–4 K^–1) and the fractional free volume (2.8% to 10.4%) were estimated. The DB curves were fitted by a sum of three Gaussians, the narrowest of which is assumed to represent the self-annihilation ofp-Ps localised at holes. The intensity of the narrow component,I _n, varies between 0 and 7.3% in a similar way as the LT intensityI _4/3 varies. From this it was concluded that other Ps reactions beside pick-off are not important. Further, it was shown that the average positron lifetime is dominated by theo-Ps component,T _{4 g}, while the behaviour of the DB peak height is mainly affected by thep-Ps narrow componentI _n .     

A 2pπ, 3dπ valence bond wave function for the 1B1u state of ethylene

A 2p, 3d valence bond wave function for the lowest ¹ B _1u state of the -system of ethylene is variationally optimized with respect to the atomic orbital exponents using a non-empirical -approximation. The resulting energy compares favourably with previous calculations and leads to a satisfactory value for the lowest ¹ A _1g-¹ B _1u transition energy. The optimized exponent for the 2p orbital is close to the Slater value whereas the exponent for the 3d orbital is found to be nearly hydrogenic. The implications of this result are discussed in some detail.

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Zusammenfassung Für den tiefsten ¹ B _1u -Zustand des -Elektronensystems des Äthylens wird nach der Variations-methode eine 2p, 3d-Valenzbindungs-Wellenfunktion bezüglich der Orbitalkoeffizienten optimiert, wobei eine nicht-empirische -Approximation zugrunde gelegt wird. Die berechnete Energie stimmt gut mit den Ergebnissen vorausgegangener Rechnungen überein. Für den tiefsten ¹ A _1g ¹ B _1u -Übergang ergibt sich ein befriedigender Energiewert. Der optimierte Orbitalkoeffizient für das 2p-Orbital stimmt gut mit dem nach der Slaterschen Regel bestimmten Koeffizient überein, während man für den 3d-Orbitalkoeffizienten einen Wert findet, der dem des Wasserstoffs ähnlich ist.

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Résumé Une founction d'onde V.B.(2p , 3d ) est optimée pour l'état ¹ B _1u d'aethylen. L'energie calculé aussi que l'energie de transition la plus basse ¹ A _1g -¹ B _1u est en bon accord avec des valeurs connues.

     

Diatomic interactions in momentum space. The 2pπ u and 3dπ g states of H 2 + system

The recently proposed method of momentum electron density for interatomic interactions is applied to the two states of the H ₂ ⁺ system. The processes of the attractive 2P _u and repulsive 3d _g interactions are analysed based on the behaviour of the momentum density and Compton profile. The results are compared with the previous ones for the 1 _{S g} and 2p _u states. The guiding principle of contraction and expansion for the energy-density relation in momentum space is shown to be common to both the and states.     

Transference numbers of aqueous HCl up to 15 mol-kg−1 at 25°C: A systematization and reassessment

Ion-transfer parameters of aqueous hydrochloric acid over a wide molality range have been re-investigated taking the concurrent solventtransfer into due account. In this context, the transference numbers for the hydrogen ion _H and for water _w have been determined from 10^–2 to 15 mol-kg^–1, together with the corresponding infinite-dilution values _H ^o and _w ^o , by processing a set of nearly a hundred emf measurements (some twenty of them new for this work) on HCl concentration cells with transference with both cation-reversible and anion-reversible electrode pairs.     

Effect of the Reaction Products on the Rate of Oxidation of Crotonaldehyde

Study of the oxidation of crotonaldehyde revealed an appreciable inhibitory effect of the products on the process. Analysis of the kinetic data obtained over a wide range of reaction conditions (c ₀ 1.5-3.3 M, pO₂ 1-16 atm, T 293-309 K) showed that the overall oxidation process (with account taken of the inhibitory effect of the products) is described by the equation: W _CA = k*_ap c _CA (pO₂)^0.6 (1 + 0.17c _CA)^{- 1}, where k*_ap is the apparent rate constant, and c _CA is the decrease of the aldehyde concentration by a moment .     

Transient photocapacitance study in 4-nitro-4′-aminodiphenyl layers

In 4-nitro-4-aminodiphenyl (NAD) layers the photocapacitance (PhC) transients were investigated. PhC spectral distribution as well as the temperature dependences of time constants (under/_on/or after/_off/illumination) have been measured. The photocapacitance spectral distribution possesses maxima at 350, 500, and 750 nm. It was shown that _on (T) is of exponential form while _off (T) is more complicated. The values of thermal activation energies (0.65±0.05) eV of both time constants coincide. The mechanism of photocapacitance process has been disclosed in NAD layers.     

Temperature deactivation of excited Tb3+ in the presence of 1,2-dioxetane in acetonitrile

Quenching the fluorescence (FL) of terbium perchlorate by 2,2-adamantane-2,2-dioxide (1) was shown to have a chemical character and was caused by the formation of the [1...Tb³⁺] complex. The dependence of the lifetime () of FL of Tb^*3+ in acetonitrile on the temperature and concentration of1 has been studied. The temperature dependence of is caused by a rearrangement of the inner sphere of the aquasolvate complexes of Tb³⁺, which leads to the replacement of H₂O with MeCN and1. The energy of replacing the H₂O molecule in the inner sphere of complexes with a solvent molecule has been calculated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1762–1766, October, 1994.     

Photophysical properties of (η2-C60)Pd(PPh3)2 complex in benzene. Picosecond and nanosecond laser photolysis

Absorption spectra of the photoexcited (²-C₆₀)Pd(PPh₃)₂ complex in benzene were obtained by picosecond and nanosecond laser photolysis. The spectra are compared with those observed for photoexcited states of fullerene C₆₀ and charge-transfer states of C₆₀ complexes with ternary amines. The relaxation kinetics of excited (²-C₆₀)Pd(PPh₃)₂ complex has three components with characteristic lifetimes ₁ = 43 ps, ₂ = 1500 ps, and ₃ = 1.17 s. The results are discussed in terms of the four-level scheme of the excited complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1163–1166, May, 1996.     

Tensor polarizabilities of the 4f 7(8 S)5d6s 2 9 D 2,3,4,5,6 levels in Gd I

The optical pumping method with rf detection and the nonlinear level crossing technique were used in parallel electric and magnetic fields to investigate the Stark splitting of all the fine structure levels of the ground multiplet 4f ⁷ (⁸ S) 5d6s ^{2 9} D in Gd I. The tensor polarizabilities were deduced from the level crossing and the rf signals. The variation of the tensor polarizabilities is well reproduced by the LS coupling approximation, except for the small value of the⁹ D ₅ level. A value of the tensor polarizability of the 5d electron is evaluated from the experimental results, ₂(5d)=2.00(6) kHz(kV/cm)². It is shown that the ratio between the electric quadrupole constant and the tensor polarizability is constant, except for the⁹ D ₅ ratio, which is caused by a breakdown of the central field model.     

Change in the reactivity of di-tert-butyl peroxide during homolysis with an increase in the degree of conversion and pressure

It was found that the differential reactivity (k _d ) of di-tert-butyl peroxide (DTBP) in a solution of 2-methoxy-(1) and 2-ethoxytetrahydropyran (2) at 130°C and pressuresp=20 and 1000 MPa is a periodic function of the degree of conversion, arbitrarily measured by the concentration oftert-butyl alcohol (TBA) formed. The functionk _d =F([TBA]) was calculated with the spline approximation (SA) of the experimental [TBA] as a function of the reaction time , giving a continuous curve of d[TBA]/d as a function of . The integral reactivityk _d =G([TBA]) calculated with the kinetic equation for a first-order reaction for decomposition of DTBP in1, 2, 1 + C ₆ H ₆ and2 + C ₆ H ₆ in three segments of in the range ofp=20–1000 MPa changes differently with an increase in the degree of conversion for differentp. The volume activation effects ( ) determined by SA of the experimental lnk _d as a function ofp were calculated for close degrees of conversion, [TBA]=0.1–0.14M. The as a function ofp obtained were compared with the similarly processed published data on decomposition of DTBP inn-heptane and dicumyl peroxide (DCP) in different aromatic solvents. The results were attributed to the effect of the type of packing of the solvent molecules surrounding the reacting molecule on the reactivity of the peroxide and not to the effect of radical recombination in the primary cage.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 829–837, April, 1992.     

The transition time for the ground state hyperfine splitting of209Bi82+

The lifetime of the excited hyperfine state of the ground state level of²⁰⁹Bi⁸²⁺ is calculated. The result of (Bi⁸²⁺)=400.09 s still exhibits a discrepancy to the experimental value ^ex=351(16) s of about 14%.