A coupled-states approximation study of Li+-H2 collisions

The recently developed coupled-states approximation for describing atom-molecule collisions is applied in a slightly modified form to the Li⁺-H₂ system. Due to the large anisotropy in the potential, a preferred orientation for rotational excitation exists which suggests the use of l = J-j rather than l = J as the angular momentum quantum number in approximating the eigenvalue of 1² by l(l + 1). Here, J and j are respectively the total and rotator angular momentum quantum numbers. The coupled-states integral and differential cross sections are compared with results of close-coupling calculations at 0.6, 0.9, and 1.2 eV.     

l-splitting of energy levels for almost coulombic central potentials

An operator which for purely Coulomb problems acts as a raising operator for the total angular momentum is employed to provide an expression for the l-splitting due to the non-coulombic part of an arbitrary central potential. Both bound and continuum states are examined. Several useful approximate forms are also obtained and tested.     

Alignment and orientation effects in resonant charge exchange from laser excited Na*(3p)

A collisional alignment and orientation study with planar symmetry is described, determining the complete density matrix for resonant charge transfer from laser excited atoms. Results are reported for the Na⁺+Na*(3p) system over the collision energy rangeE _c.m.=50?100 eV. We communicate the optimal alignment angle γ and linear polarisationP _l ⁺ of the charge cloud as well as its relative height ρ₀₀ and the angular momentumL _⊥ ⁺ transferred in the collision as a function of the scattering angle. For preparation of the sodium 3p orbital in the scattering plane (positive reflection symmetry) we observe that at small reduced scattering angles (<20 eV°) the preparation of apσ at large internuclear distances contributes most to the scattering intensity whereas at larger reduced scattering angles (>60 eV°) apπ⁺ preparation is more important. In contrast, preparation of thepπ^? orbital (perpendicular to the scattering plane) is large at small and vanishes at larger scattering angles. We conclude that orbital following cannot be assumed in this resonant charge transfer process. The angular momentum transfer is observed to be small, indicating only little coherence in the process, but shows nevertheless an interesting behaviour as a function of scattering angle.     

Measurement of state-to-state rotational transfer rates in collision of I2*(B 0u+, υ = 15, j) with 3He, 4He,Ne, Ar,H2, D2 and I2

The selective laser excitation and induced fluorescence observation technique has been used to study rotationally inelastic collisions of I₂^*(B 0_u⁺, υ = 15,j) with I₂, ³He, ⁴He, Ne, Ar, H₂ and D₂. For each collision partner, several initial rotational levels ranging from j_i = 12 up to j_i = 146 have been excited. For purely rotational transfer within the υ = 15 level, our data are perfectly consistent with energy sudden (eventually corrected) scaling laws. Thus, any thermally averaged rate constant, k(j_i → j_f), can be expressed as a function of the basis rate constants k(l → 0). Furthermore, these k(l → 0) are found to follow simple empirical fitting laws. Consequently any k(j_i → j_f) can be predicted given a set of two or three fitting parameters. Collisions with relatively heavy particles (I₂, Ar and Ne) are well described by using the inverse power fitting law k(l → 0) = b[l(l+1)]^?γ, where b = 1.7, 1.2 and 1.2×10^?10 cm³ s^?1 and γ = 1.08, 1.02 and 1.17 for I₂^*-Ne, I₂^*-Ar and I₂^*-I₂ collisions respectively. For collisions with light particles (³He, ⁴He, H₂ and D₂), k(l → 0) shows a sharp decrease with l which can be accounted for by a hybrid power-exponential fitting law k(l → 0) = b[l(l+1)]^?γ exp[-l(l+1)/l^* (l^*+1)], where b = 0.84, 0.71, 2.77 and 2.78×10^?10 cm³ s^?1l⁺ = 20.6, 23.1, 18.8 and 31.4, and γ = 0.66, 0.66, 0.78 and 0.91 for I₂^*-³He, I₂^*-He, I₂^*-H₂ and I₂^*-D₂ collisions, respectively. We confirm that the rotational transfer dynamics in heavy molecules is mainly governed by angular momentum exchange.     

Photodissociation kinematics. II. Laboratory angular distributions of a hydride model system and the kinematic isotope effect

In the study of photodissociation processes, a theoretical framework of the laboratory angular distributions of photofragments has been firmly established. Numerical calculations of

, which is the radial-rotational coupling coefficient in a quantum-mechanical center-of-mass to laboratory-frame transformation, are implemented in this report. The general behavior of

as a parametric function of l, l₁, l₂ and x is explored. To illustrate the calculation of the laboratory angular distributions in a photodissociation process, a hydride model system is chosen. The parametric dependences of the photofragment's angular distribution on the initial linear momentum, recoil momentum and the angular momentum of the repulsive state are demonstrated in these numerical calculations. The laboratory angular distributions of photodissociated hydrogen and deuterium atoms exhibit a kinematic isotope effect.     

Stark manifolds of barium Rydberg states

In a CW laser-atomic beam experiment Stark manifolds in barium originating from the Rydberg states 6s40f ¹ F ₃, 6s40g ^1,3 G ₄,³ G ₅ and 6s40h ^1,3 H ₅ have been studied. Accurate quantum defect values for higher orbital angular momentum states (l=6, 7) have been determined. The Stark manifolds are also calculated by diagonalization of the energy matrix in the presence of an external electric field. Good agreement between experiment and calculations is obtained.     

Retardation (Casimir) energy shifts for Rydberg helium-like low-Z ions

The development of storage rings and electromagnetic traps for heavy charged particles is opening up new regimes of atomic physics, including, in particular, spectroscopic studies of Rydberg helium-like ions — with nuclear chargeZ, one electron in the 1s state, and one electron in a near-hydrogenic state of highn andl <n, withn andl the principal and orbital quantum numbers, respectively. We consider the possibility of detecting energy shifts due to retardation, ΔE _ret (n,l), Casimir-like effects. These are quantum electrodynamic (QED) retardation effects associated with the finite speed of light. (As opposed to basically kinematic and dynamic QED effects for small quantum numbersn andl, the appropriate expansion parameter forn andl large for retardation QED corrections is notZ(e ²/?c) but [(Z ? 1)/n ² Z ²](?c/e ²).) We wish to provide some orientation to those planning experiments in the area, with regard to the choices ofn,l, andZ most likely to be able to generate a high-precision confirmation of a retarded interaction. To do so, we provide extensive tables of estimates, for 1s,nl states, of ΔE _ret(n,l), of radiative widths, and ofE, the spin-independent (“electric” fine structure) energy in the absence of retardation shifts, for (nuclear spin zero) ions withZ=2, 6, 8, 16 and 20. These ions might be experimentally accessible in storage rings, and theZ's are low enough that virtual pair production effects may not yet be significant. There is also a brief survey of possible experimental techniques.     

Determination of residual chlorine by derivatisation with 2,6-dimethylphenol and gas chromatographic separation

Residual chlorine in aqueous solution is converted to 4-chloro-2,6-dimethylphenol, which is extracted into hexane and determined by gas chromatography. Relative standard deviations (n = 5) are 0.36–1.1% for chlorine concentrations of 8.6–0.01 mg l^-1 and chlorine recoveries are 99.2–101%. In the presence of dichromate (30 mg l^-1), relative standard deviations (n = 5) are 1.19–2.71% for chlorine concentrations of 9.3–0.1 mg l^-1. Oxidants and coloured solutes do not interfere.     

Even-parity auto-ionizing states of iridium I observed by resonance laser ionization spectroscopy

Auto-ionizing states of neutral iridium were observed in the continuum structure near the first ionization limit using one-color and two-color two-step resonance laser ionization spectroscopy. The total angular momentum of 20 even-parity auto-ionizing states could be determined from a combined analysis of the two-color spectra obtained with ionization schemes using intermediate states with different total angular momentum. Double-resonant ionization schemes were evaluated by fluence-dependence measurements, and photo-ionization cross-sections for resonant ionization transitions were determined. We could also identify several high-lying members of ns, np and nd Rydberg series converging to the first ionization limit of the atom.     

Theory for spin relaxation in small magnetic metal clusters

We discuss the magnetic properties of small neutral transition-metal clusters like Fe _n and Co _n deduced from Stern-Gerlach deflection experiments. We claim that the asymmetric Stern-Gerlach deflection profiles are due to a transfer from electronical angular momentum to the cluster rotation, allowing for a depopulation of the high energy magnetic levels. For finite temperatures we consider two limiting cases. First, the cluster magnetization is assumed to be tied to the random orientation of the cluster easy axes due to the lattice anisotropy. This causes a surprisingly small magnetization for small external magnetic fields. For larger fields and also for increasing temperatures the magnetization is released from the cluster geometry and allowed to align itself parallel to the field. In the second case the clusters are treated as an ensemble of superparamagnetic particles. Here, the effect of the anisotropy is less visible. The cluster lattice anisotropy per atom is expected to decrease for increasing cluster size. Preliminary results support this.     

Magnetic-sublevel differential cross sections for electron-impact excitation of He n1P levels: Theory and experiment in natural and atomic coordinate frames

Experimental data for the average transferred angular momentum, 〈_⊥〉, have been combined with experimental differential cross section [DCS] data for electron impact excitation of the 2¹ P and 3¹ P levels of helium to obtain the individual magnetic-sublevel differential cross-sections, [DCS _M ⁿ ], in the natural (and atomic) coordinate system. First-order many-body theory (FOMBT) has been used to obtain corresponding theoretical predictions for DCS _M ⁿ which are compared to these results. This comparison shows that FOMBT generally predictsM=+1 sublevel excitation DCS better than that forM=?1.     

Indirect processes in the electron-impact ionization of Li-like ions

Detailed measurements of electron-impact ionization cross sections have been made in the vicinity of the excitation-autoionization thresholds of Li-like B²⁺, C³⁺, N⁴⁺, O⁵⁺ and F⁶⁺ ions. With an energy spread of 0.4 to 1% of the electron energy and statistical uncertainties as low as 0.1% we could clearly resolve thresholds for excitation of individual terms in 1s2s2l configurations. Numerous resonance features were found which are due to dielectronic capture of the incident electron with subsequent two-electron emission. In particular, dielectronic capture processes involving Δn=2 excitations of a 1s electron provide the dominant resonance contributions to the measured cross sections. Rydberg series 1s2snln′l′ of resonances withn=3 (Δn=2) andn=4 (Δn=3) are resolved up to principle quantum numbersn′ equal to 6 or 7.     

Tables of vacuum polarization of excited states of light mesic atoms

We present tables of vacuum polarization energies for light mesic atoms (p,d,³He and⁴He) with a precision of 10^?4 for all values ofn andl.     

Eigenstates from the discretized path integral

A numerically convenient and accurate method for evaluating eigenstates of a quantum system with an arbitrary angular momentum (l) is proposed using the discretized version of the path integral. The accuracy of the method is examined by comparing the calculated results with analytical solutions for simple systems.     

The effect of the electron spin on angular momentum transfer in Na*(32 P 3/2)+Na+ collisions — crossed beam experiment and semiclassical calculation

The angular momentum transfer between electronic and heavy particle motion has been studied for inelastic collisions of laser state-prepared Na*(3² P _3/2,M _J ) with Na⁺ leading to Na*(3² D) or Na(3² S) in the energy rangeE _cm=5?47.5 eV. The measurements are compared to semiclassical calculations employing the coupled channel method in the impact parameter approximation but including dynamics of the electron spin coupling to the heavy particle motion.     

Determination of aluminium in blood plasma or serum by electrothermal atomic absorption spectrometry

A carbon-furnace atomic absorption method is used to determine aluminium in blood serum or plasma, diluted (1 + 2) with purified water prior to injection (20 μl) into the furnace. Procedures are described to reduce contamination during sample collection, storage and preparation of samples. A study of the interferences of inorganic ions shows that the temperature programme developed minimises these, allowing the use of aqueous standards for calibration. Ashing at 1400°C, prior to atomisation, also removes non-specific background effects, and optical correction is not required. A sample throughput of 50 duplicate analyses per day is possible and the precision (between batch) at 24 μg Al l^-1 was 11.2% (n = 10) and at 340 μg Al l^-1 was 6.3% (n = 18). Down to 4 μg Al l^-1 can be determined. Reference values for a healthy population were 4.1–20 μg Al l^-1 (mean 10.2).     

Enthalpies of transfer of amino acids from water to aqueous solutions of sodium nitrate and sodium perchlorate at T = 298.15 K

Enthalpies of solution of glycine, l-alanine and l-serine in water and aqueous solutions of NaNO₃ and NaClO₄ have been determined at T = 298.15 K with a calorimeter. Enthalpies of transfer (Δ_trH) from water to aqueous solutions of salts were derived and interpreted in terms of electrostatic interaction and structural interaction. Δ_trH decreases with increasing salt concentration in the composition range studied. The transfer enthalpies of amino acids from water to NaNO₃ solution and low concentration NaClO₄ solution vary in the sequence l-serine < glycine < l-alanine while glycine < l-serine < l-alanine in NaClO₄ solution above 2 mol kg⁻¹. The difference may be due to ion association at high concentration, weakening the interaction with l-serine more than with glycine.     

Spin density distribution in oxamato-type transition metal complexes

The spin density distribution of the paramagnetic [ⁿBu₄N]₂[Cu(dana)] dana = N,N′-(naphthalene-2,3-diyl)-bis(oxamato) has been derived from angular dependent electron paramagnetic resonance measurements at room temperature. The results indicate a noticeable spin density transfer from the central metal to the coordinated N and O atoms. Quantum chemical studies using density functional theory reinforce the results.     

Bases for the irreducible representations of O(3) symmetry adapted to a crystallographic point group

We construct bases for the irreducible representations of the rotation group O(3) which are symmetry adapted to a Crystallographic point group. We obtain explicit expressions for the cubic groups, which are valid for arbitrary values of the angular momentum quantum number l. Our method yields an efficient algorithm for both analytical and numerical work. An explicit formula for the multiplicities of an irreducible representation for the cubic groups in an arbitrary angular momentum term l is also derived.     

Cation Recombination Energy/Coulomb Repulsion Effects in ETD/ECD as Revealed by Variation of Charge per Residue at Fixed Total Charge

Electron capture dissociation (ECD) and electron transfer dissociation (ETD) experiments in electrodynamic ion traps operated in the presence of a bath gas in the 1–10 mTorr range have been conducted on a common set of doubly protonated model peptides of the form X(AG)_nX (X = lysine, arginine, or histidine, n?=?1, 2, or 4). The partitioning of reaction products was measured using thermal electrons, anions of azobenzene, and anions of 1,3-dinitrobenzene as reagents. Variation of n alters the charge per residue of the peptide cation, which affects recombination energy. The ECD experiments showed that H-atom loss is greatest for the n?=?1 peptides and decreases as n increases. Proton transfer in ETD, on the other hand, is expected to increase as charge per residue decreases (i.e., as n increases). These opposing tendencies were apparent in the data for the K(AG)_nK peptides. H-atom loss appeared to be more prevalent in ECD than in ETD and is rationalized on the basis of either internal energy differences, differences in angular momentum transfer associated with the electron capture versus electron transfer processes, or a combination of the two. The histidine peptides showed the greatest extent of charge reduction without dissociation, the arginine peptides showed the greatest extent of side-chain cleavages, and the lysine peptides generally showed the greatest extent of partitioning into the c/z?-product ion channels. The fragmentation patterns for the complementary c- and z?-ions for ETD and ECD were found to be remarkably similar, particularly for the peptides with X = lysine.