Lineshapes of the even mp1/2 5n(p′/f′) autoionizing resonances of Ar, Kr and Xe

The even parity mp_1/2 ⁵np^′ and mp_1/2 ⁵nf^′ autoionizing resonances of Ar, Kr, and Xe (m=3,4,5) were investigated experimentally and theoretically by one-photon excitation from lower-lying intermediate levels. In particular, high resolution measurements for the Ar(nf^′), Kr(12p^′,8f^′), and Xe(8p^′) resonances are reported; lineshape parameters for these resonances have been derived by a Fano-type analysis, thus yielding reduced resonance widths. The experimental spectra and the resonance parameters are compared with theoretical calculations which are based on the configuration interaction Pauli–Fock approach including core polarization. The measured and calculated lineshapes are in good agreement. In addition, theoretical predictions are presented for other resonances, which have not yet been observed experimentally, and some systematic trends are elucidated.     

Structure of water-in-oil microemulsions of AOT by infrared spectroscopy

Summary The structure of water in water/AOT/n-heptane reverse micelles has been studied as a function of the [H₂O]/[AOT] ratio (W) by using the absorption IR due to O−H stretching modes in the 3800–3000 cm⁻¹ range. The results show that the IR spectra can be expressed as a sum of contributions from bound- and bulk-like water. The fraction of water in the two ?regions? within the water pool was evaluated as a function ofW. The ?bound? water region seems to hold 3.5 water molecules (corresponding to 7 O−H oscillators) per AOT molecule and its formation is nearly complete atW>6. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Energies and electron correlation effects in two-electron doubly excited (nl)2 states

Energies of singlet doubly excited states 2p^{2 1}D, 3d^{2 1}G, 4f^{2 1}I of He isoelectronic series are calculated in the framework of the variational method by using Hylleraas-type wave functions and a real Hamiltonian. The results obtained show quantitatively the importance of electron correlation effects in the doubly excited states and they are in good agreement with some experimental data and other theoretical results. Received 30 March 2000 and Received in final form 4 July 2000     

Properties of doubly excited states of H- and He associated with the manifolds from N = 6 up to N = 25

This paper discusses theory and results on ¹P⁰ doubly excited states (DES) in He and in H^- of very high excitation, up to the N = 25 manifold. Our calculations employed full configuration interaction (CI) with large hydrogenic basis sets and produced correlated wavefunctions for the four lowest roots at each hydrogenic manifold by excluding open channels and the small contribution of series belonging to lower thresholds. The suitability of the hydrogenic basis sets for such calculations is justified, apart from their practicality, by the fact that, by computing from them natural orbitals, the results were shown to be the same with those of earlier multiconfigurational Hartree-Fock (MCHF) calculations on low-lying DES. In total, 160 states were computed, most of them for the first time. Their energy spectrum should be of use to possible future photoabsorption experiments. For certain low-lying DES up to N = 13, for which previous reliable results are available, comparison of the calculated energies shows good agreement. The correlated wavefunctions contain systematically chosen single and double excitations from each hydrogenic manifold of interest. From their analysis, we determined the “goodness" of different quantum numbers and the geometry (average angles and radii) as a function of excitation. For the Sinano lu-Herrick ( K , T ) classification scheme, whose basis is a restricted CI with hydrogenic functions and which has thus far been tested only on low-lying DES, we established that, whereas T remains a good index as energy increases, K does not. Consequently, a more flexible than K quantum number is needed in order to account for most of the additional correlation. This number, represented by F = N - K - 1, where N and K are not good numbers anymore, produces consistently a much higher degree of purity than the ( K , T ) scheme does, especially as N increases and as the relative significance of various virtual excitations due to electron correlation increases. Among the four states of each manifold, in all cases in H^- and in most cases in He, the three are of the intrashell type and one is of the intershell type with ( F , T ) = (0, 0). The lowest intrashell states and the lowest intershell states exhibit a wide angle geometry tending to 180 ^° as N ↦∞. Received 10 September 2001 and Received in final form 12 November 2001     

Transition wavelengths and probabilities for spectral lines of Zr III

Wavelengths and oscillator strengths for all 4d4f↦4d² dipole-allowed fine-structure transitions in Zr III have been calculated within the Multi-Configuration Dirac-Fock method with QED corrections. These transitions are included in the spectrum of some chemically peculiar stars, like the B-type star χ Lupi observed by the Hubble space telescope. The results are compared to existing experimental and semi-empirical data.     

Radiative lifetime and oscillator strength determinations in potassium ions (K V, K VI and K VII)

Oscillator strengths have been calculated for the transitions depopulating levels of the 3s²3p³, 3s3p⁴ configurations of K V, of the 3s²3p², 3s3p³ configurations of K VI and of the 3s²3p, 3s3p², 3p³ and 3s3p3d configurations of K VII. A multiconfiguration Dirac-Fock method, incorporating the relativistic two-body Breit interaction and quantum electrodynamics corrections due to self-energy and vacuum polarization, has been used for the calculations. The reliability of this approach has been tested by comparison with relativistic Hartree-Fock calculations and also with some experimental measurements performed by beam-foil spectroscopy at a beam energy of 1.7 MeV.     

Multiconfiguration Dirac-Fock calculation of transition energies in highly ionized bismuth, thorium, and uranium

Structure and QED effects for and levels are calculated for lithiumlike U⁸⁹⁺ trough neonlike U⁸²⁺, lithiumlike Th⁸⁷⁺ trough neonlike Th⁸⁰⁺ and lithiumlike Bi⁸⁰⁺ trough neonlike Bi⁷³⁺. The results of the first two sets are compared with recent measurements of the transition energy in 3 to 10-electron ions. Good agreement with experiment is found for most of the observed lines. Forty-one possible transitions are calculated for each ion in the eight ionization states, in the experimental energy range. Twenty-eight of these transitions have not been observed, nor calculated previously. We also calculate transition rates, branching ratios, excitation and ionization cross sections and confirm that the thirteen experimental o bserved transitions correspond to the ones with highest relative intensities. However, we find nineteen more transitions that could be measured in a more sensitive experiment. Received: 5 November 1997 / Accepted: 8 December 1997     

A complete active-space self-consistent-field study on cubic N8

Summary Complete Active-Space Self-Consistent-Field (CAS-SCF) calculations for cubic N₈ are presented. We studied the N₈↔4N₂ reaction inD _4h symmetry and found its energy release and activation barrier with three different atomic basis sets. The energy release for this reaction is predicted to be around 526 kcal/mol, while the energy barrier to dissociation is estimated about 159 kcal/mol. These results are in substantial agreement with previousab initio estimates. The authors of this paper have agreed to not receive the proofs for correction.     

Decay of metastable states in Nd II

The difficulty associated with an accurate determination of transition rates for forbidden lines in lowly ionized heavy elements is illustrated in the case of Nd II. We have investigated the radiative decay of the low-lying metastable levels in Nd⁺ including the two levels K_11/2 and I_13/2. In these two particular cases, using different theoretical approaches, we find that the decay is dominated by the M1 channels but that the E2 contributions are of the same order of magnitude. These levels have also been studied experimentally by lifetime measurements with the heavy ion storage ring CRYRING of Stockholm University. The difficulties encountered when performing such experiments are underlined and discussed.     

QED and relativistic corrections in superheavy elements

In this paper we review the different relativistic and QED contributions to energies, ionic radii, transition probabilities and Landé g-factors in super-heavy elements, with the help of the MultiConfiguration Dirac-Fock method (MCDF). The effects of taking into account the Breit interaction to all orders by including it in the self-consistent field process are demonstrated. State of the art radiative corrections are included in the calculation and discussed. We also study the non-relativistic limit of MCDF calculation and find that the non-relativistic offset can be unexpectedly large.     

The ground state and doubly-excited <Superscript>1,3</Superscript>P° states of hot-dense plasma-embedded Li<Superscript>+</Superscript> ions

We have investigated the ground state and the doubly excited ^1,3P^○ resonance states of plasma-embedded Li⁺ ion. The plasma effect is taken care of by using a screened Coulomb potential obtained from the Debye model. A correlated wave function has been used to represent the correlation effect between the charged particles. The ground state of Li⁺ in plasmas for different screening parameters has been estimated in the framework of Rayleigh-Ritz variational principle. In addition, a total of 18 resonances (9 each for ¹P^○ and ³P^○ states) below the n=2 Li⁺ thresholds has been estimated by calculating the density of states using the stabilization method. For each spin state, this includes four members in the 2snp₊ (2≤n ≤5) series, three members in the 2snp_- (3≤n ≤5) series, and two members in the 2pnd (n=3, 4) series. The resonance energies and widths for various Debye parameters ranging from infinity to a small value for these ^1,3P^○ resonance states along with the ground state energies of Li⁺ and the Li²⁺ (1S), Li²⁺ (2S) threshold energies are reported. Furthermore, the wavelengths for the photo-absorption of lithium ion from its ground state to such ¹P^○ resonance states for different Debye lengths are also reported.     

Ab initio correlation approach to a ferric wheel-like molecular cluster

We present an ab initio study of electronic correlation effects in a molecular cluster derived from the hexanuclear ferric wheel [ LiFe₆(OCH₃)₁₂-(dbm)₆] PF₆. The electronic and magnetic properties of this cluster have been studied with all-electron Hartree-Fock, full-potential density functional calculations and multi-reference second-order perturbation theory. For different levels of correlation, a detailed study of the impact of the electronic correlation on the exchange parameter was feasible. As the main result, we found that the influence of the bridge oxygen atoms on the exchange parameter is less intense than the influence of the apical ligand groups, which is due to the geometry of the cluster. With respect to the cluster model approach, the experimental value of the exchange parameter was affirmed.     

Fine structure in 14C cluster emission from 225Ac

A fine structure in the ¹⁴C decay of ²²⁵Ac is predicted quantitatively by accounting dynamical aspects during the disintegration process. Transitions to the excited states of the daughter nucleus are considered to be mainly directed by the Landau–Zener promotion mechanism in the region of avoided crossing levels. The level scheme is evaluated with the superasymmetric two–center shell model. The half–lives are computed considering the cluster decay as a superasymmetric fission process. Received: 31 July 1998 / Revised version: 27 November 1998     

Atomic Compton profiles within different exchange-only theories

The impulse Compton Profiles (CPs) J(q) and the expectation values for some inert gas atoms (He-Kr) are computed and compared within the Harbola-Sahni (HS), Hartree-Fock (HF) theories and a Self-Interaction-Corrected (SIC) density functional model. The Compton profiles for excited states of helium atom are also calculated. While the calculated CPs are found to generally agree, they differ slightly from one another for small values of the Compton parameter q and are in good agreement for large q values. The expectation values within the three theories are also found to be comparable. The HS formalism is seen to mimic HF reasonably well in the momentum space, establishing the logical consistency of the former. Received: 11 December 1998 / Received in final form: 20 April 1999     

Quadruply excited beryllium-like atoms – a semiclassical model

The semiclassical spectrum of quadruply highly excited four-electron atomic systems has been calculated for the plane model of equivalent electrons. The energy of the system consists of rotational and vibrational modes within the circular skeleton orbit approximation, as used in a previous calculation for the triply excited three-electron systems. The full dynamical analysis is carried out within the Hamiltonian theory, accounting for the inertial effects and the complete coupling between different degrees of freedom. Here we present numerical results for energy spectrum of the beryllium atom. The lifetimes of the semiclassical states are estimated via the corresponding Lyapunov exponents. The vibrational modes relative contribution to the energy levels rises with the degree of the Coulombic excitation.     

Dynamical study of the Cs<Superscript>+</Superscript>(<Superscript>1</Superscript>S<Subscript>0</Subscript>)+Mg(3 <Superscript>1</Superscript>S<Subscript>0</Subscript>) non adiabatic collision system in the few keV energy range

The dynamics of collisional processes between Mg atoms and caesium ions is studied using the hemiquantal (HQ) approach with special attention to the collisional channels leading to Mg(3 ¹P) and Cs(6 ²P) states, for which the corresponding emission excitation functions have been previously measured in our laboratory. The radial and angular non-adiabatic couplings between the manifold of quasimolecular states have been determined using an ab initio configuration interaction calculation. The cross-sections for the different channels, as a function of the laboratory collisional energy, are compared with experimental values. The dynamical calculations indicate that, for the inelastic processes considered, the range of relevant impact parameters is small, active collisions being of the head-on type. .     

Screening constant by unit nuclear charge calculations for (n s2)1Se, (np2)1De and (N s n p)1P○ excited states of He-like systems

Screening Constant by Unit Nuclear Charge (SCUNC) is a new analytical method suitable for the treatment of the properties of He-like systems. In this paper, the possibilities of the method are demonstrated for calculating in the framework of semi-empirical procedure, total energies, total electron-electron interaction energies and excitation energies for (ns²)¹S^e, (np²)¹D^e and (Nsnp)¹P° doubly excited states of He-like ions. The proposed semi-empirical scheme, leads to accurate results in good agreement as well as with available other theoretical results than experimental data.     

Long-range correlation energies calculations for π electronic systems

A simple formula for correlation energy E_c of the π electron systems is obtained under an approximation for the electron-electron interactions. This formula is related directly to square of the bond order matrix and the nearest-neighbor Coulomb electron-electron interaction. The influence of the correlation energy on the band energy gap is discussed. The values of the correlation energy for polyacetylene (PA) are calculated and can be compared with those for PA obtained by other methods, including ab initio method.     

Variational calculation of some S-states of Coulomb three-body systems

A generalized Hylleraas-type basis set with three nonlinear parameters is proposed to study three-body systems interacting via coulomb forces within the framework of non-relativistic quantum mechanics. This basis set improves the rate of convergence with respect to previous ones, specially for non-symmetric systems and excited states of two electron atoms. Accurate binding energies and other properties for S-states of helium-like ions, muonic molecules and the positronium negative ion are reported. Received 21 July 2000 and Received in final form 4 October 2000     

Ab initio calculations of the second dynamic hyperpolarizability of LiH by means of Floquet theory approach

Floquet theory is used to describe the response of a molecule to applied radiation electric field. The method of ab initio calculation of frequency dependent (hyper)polarizabilities based on combination of perturbation theory with the finite field method has been developed. Electron correlation is taken into account by means of the CIPSI algorithm. The total wave function expansion involves spectral, pseudo-spectral states and polynomial terms. The developed approach is applied to the calculation of the second hyperpolarizability of the lithium hydride molecule subjected to the superposition of harmonic and static electric fields. The method can be used to calculate the higher order nonlinear properties of molecules. Received 23 November 2000 and Received in final form 25 March 2001