KX-ray production cross sections for heavy target elements and14N,40Ar projectiles above the coulomb barrier

KX-ray production cross sections have been measured for beams of¹⁴N at 92, 103, 115 and 180 MeV and⁴⁰Ar at 180 and 300 MeV on targets with atomic numbers ranging from 40 to 90. We find that the measured values can be well reproduced with a plane wave Born calculation, provided that corrections for the Coulomb deflection of the projectile, the increased binding energy of theK-shell electron and relativistic effects of theK-shell wave function are taken properly into account.     

K-shell ionization induced by 30 MeV/u argon and neon beams

We have studiedK-shell ionization induced by 30 MeV/u Ne and Ar projectiles on target atoms with atomic numbers ranging from 27 to 90. X-ray production cross sections and energy shifts were measured with Si(Li) detectors. In most cases satisfactory agreement between measurements and theoretical direct ionization cross sections is obtained when the contribution of electron capture is included. The influence of multiple ionization on the fluorescence yield ω _K is discussed.     

Normalization and Fermi–Coulomb and Coulomb hole sum rules for approximate wave functions

For approximate wave functions, we prove the theorem that there is a one‐to‐one correspondence between the constraints of normalization and of the Fermi–Coulomb and Coulomb hole charge sum rules at each electron position. This correspondence is surprising in light of the fact that normalization depends on the probability of finding an electron at some position. In contrast, the Fermi–Coulomb hole sum rule depends on the probability of two electrons staying apart because of correlations due to the Pauli exclusion principle and Coulomb repulsion, while the Coulomb hole sum rule depends on Coulomb repulsion. We demonstrate the theorem for the ground state of the He atom by the use of two different approximate wave functions that are functionals rather than functions. The first of these wave function functionals is constructed to satisfy the constraint of normalization, and the second that of the Coulomb hole sum rule for each electron position. Each is then shown to satisfy the other corresponding sum rule. The significance of the theorem for the construction of approximate “exchange‐correlation” and “correlation” energy functionals of density functional theory is also discussed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

An ab initio calculation of K-spectra in molecules HCl and HF

An ab initio calculation of energies and intensities of K-emission and K-absorption spectra in molecules HCl and HF are carried out. An electronic readjustment due to a hole in a molecular core is taken into account. A vibrational structure of K-emission and K-absorption spectra is also calculated. The calculation shows that it is possible to detect a vibrational structure of valence bonding levels in X-ray emission spectra. A good agreement with experiment is obtained.     

Two and three photon dissociation of SbBr3 and a statistical interpretation of the fragmentation

It is shown experimentally that in the soft X-ray region a large circular dichroism in the photoelectron angular distribution (CDAD) exists for both valence orbitals and core levels of CO molecules adsorbed on Pd(111). From theoretical consideration it follows that in the case of a spherically symmetric ground state wave function, like the 1 and 2 orbitals of CO, CDAD appears due to the lack of spherical symmetry in the final state. For carbonK-shell experimental results are compared to model calculations. Investigations at the Pd core levels proved that CDAD does also arise in X-ray photo-emission from non-magnetic crystals.     

Surfactant-Water Systems with Small Layer Rigidity Phase Stability,Defects Models and Defects Mobility in Polyoxyethylene Surfactant with Water

Abstract

Starting from recent experiments in non-ionic surfactants, we discuss various topics characteristic of low rigidity K ₁ materials. (1) The stability of the lamellar and cubic phases is studied in a simple model involving K ₂ the saddle-splay constant K ₂, and entropy terms due to the chains. We expect the lamellar phase to have a large range of existence, and the cubic phase to be of small extent. (2) We compare to cubic phases stability in large K ₁ materials. We discuss the mobility of edge dislocations on the basis of a new model of the core which involves stretching of the core layers in one dimension, and easy nucleation of pores in this region. The core extension is a characteristic length of low K ₁ materials which is much larger than de Gennes' length for microemulsions with a similar low K ₁.     

Fermi and Coulomb holes of molecules in excited states

Correlation holes of electrons with the same (Fermi hole) and different (Coulomb hole) spins in the ground (X¹Σ⁺), first (A¹Σ⁺) and second (B¹II) excited states of LiH were constructed from full configuration interaction (CI ) wave functions. It was found that the shapes of both the Fermi and Coulomb holes in these states are dependent on the location of the reference electron. When the reference electron is chosen to be close to the Li nucleus, the Fermi correlation results in a large negative hole for all three states. However, the A¹Σ⁺ excited state is further characterized by displaying a second hole around the H nucleus, and in the B¹II state, the hole is elongated along the molecular axis. Coulomb correlation shows up strongly in the A¹Σ⁺ state and, in addition, there is clearly correlation of electrons at the two nuclei. These features of the correlation holes were compared with those from a two-Slater-determinant model wave function. The Hartree, Fermi, and Coulomb screening potentials in these states were also studied in the light of possible modeling of the correlation functionals for the excited states. © 1995 John Wiley & Sons, Inc.     

Distribution ofK α L n satellite yields for mediumZ elements bombarded with16O ions

K _α X-ray spectra were measured with a Du Mond type curves crystal spectrometer for₄₂Mo and₄₆Pd targets bombarded with oxygen ions at 5.5 MeV/u energy (i.e. at velocity closely matching those of the targetL-shell electrons). The distribution ofL-shell vacancies produced in collisions with simultaneousK-shell ionization is deduced from the measured yield distribution of theK _α X-ray satellites. The distribution shows deviations from the binomial ones. The deviations can be accounted for by assuming that theL-shell vacancy production is due to two uncorrelated processes: the direct ionization by impact and the electron capture from theL-shell of the target atom into theK-shell of the projectile, both occurring at nearly central collisions. The corresponding probability values are deduced using simple statistical considerations.     

Pseudopotential study of the ground and excited states of Yb2

The ground state of the van der Waals-type lanthanide dimer Yb₂ has been studied by means of relativistic energy-consistent ab initio pseudopotentials using three different core definitions. Electron correlation was treated by coupled-cluster theory, whereby core-valence correlation effects have been accounted for either explicitly by correlating the energetically highest coreorbitals or implicitly by means of an effective core-polarization potential. Results for the first and second atomic ionization potentials, the atomic dipole polarizability, and the spectroscopic constants of the molecular ground state are reported. Low-lying excited states have been investigated with spin-orbit configuration interaction calculations. It is also demonstrated for the whole lanthanide series that correlation effects due to the atomic-like, possibly open 4f-shell in lanthanides can be modeled effectively by adding a core-polarization potential to pseudopotentials attributing the 4f-shell to the core. Received: 3 April 1998 / Accepted: 27 July 1998 / Published online: 9 October 1998     

Angular aspects of exchange correlation and the fermi hole

The complete (nonreduced) αα probability density functions evaluated from the Hartree–Fock and simple Hartree product wavefunctions have been used to elucidate the angular features of spin correlation and the Fermi hole in the 2³S state of helium and the ground state of beryllium. This approach shows that the local Fermi holes in these two cases are very similar and that the Fermi hole is essentially spherically symmetric when the reference electron is close to the nucleus. As the reference electron is removed to larger radial distances, appreciable polarization of the Fermi hole is observed. The polarization is greater in the direction of the nucleus than away from the nucleus, contrary to the situation in the Coulomb hole of the helium ground state where the polarization is greater away from the nucleus than toward the nucleus. Several other differences between the He 2³S Fermi hole and the He 1¹S Coulomb hole are noted.     

Coulomb-Hole–Hartree–Fock functional

We have extended to molecules a density functional previously parametrized for atomic computations. The Coulomb-hole–Hartree–Fock functional, introduced by Clementi in 1963, estimates the dynamical correlation energy by the computations of a Hartree–Fock-type single-determinant wave function, where the Hartree–Fock potential was augmented with an effective potential term, related to a hard Coulomb hole enclosing each electron. The method was later revisited by S. Chakravorty and E. Clementi [Phys. Rev. A 39 , 2290 (1989)], where a Yukawa-type soft Coulomb hole replaced the previous hard hole; atomic correlation energies, computed for atoms with Z = 2 to Z = 54 as well as for a number of excited states, validated the method. In this article, we parametrized a function, which controls the width of the soft Coulomb hole, by fitting the first and second atomic ionization potentials of the atoms with 1 ? Z ? 18. The parametrization has been preliminarily validated by computing the dissociation energy for a number of molecules. A few-determinant version of the Coulomb-hole–Hartree–Fock method, necessary to account for the nondynamic correlation corrections, is briefly discussed. © 1994 John Wiley & Sons, Inc.     

Spectral change in X-ray absorption near edge structure of DNA thin films irradiated with monochromatic soft X-rays

To reveal the chemical changes induced in DNA by irradiation with ionizing radiation, we have investigated the spectral change in the X-ray absorption near edge structure (XANES) of DNA resulting from exposure to monochromatic soft X-rays. We used a thin film of calf thymus DNA as a sample and observed nitrogen K-shell and oxygen K-shell XANES spectra. The typical monochromatic soft X-ray energies used for the irradiation (395, 408, 528, and 538 eV) were obtained from a soft X-ray beamline (BL23SU, SPring-8). These energies correspond to those just below or just above the nitrogen and oxygen K-shell ionization energy, respectively. The obtained XANES spectra show significant changes by irradiation. Particularly a new π* resonance peak in oxygen XANES spectra evidently appeared by the irradiation above oxygen K-shell ionization potential. These results suggest that carbonyl groups, presumably a propenal group (OC–CC), may be produced in the sample by oxygen ionization. Thus characteristic damage induced by induction in the DNA molecule would be predicted following exposure to monochromatized synchrotron soft X-rays.     

Electronic structure of first and second row atoms under harmonic confinement

Atoms under pressure undergo a number of modifications of their electronic structure. Good examples are the spontaneous ionization, stabilization of excited-state configurations, and contraction of atomic-shells. In this work, we study the effects of confinement with harmonic potentials on the electronic structure of atoms from H to Ne. Dynamic and static correlation is taken into account with coupled cluster with single and double excitations and CASSCF calculations. Because the strength of harmonic confinement cannot be translated into pressure, we envisioned a “calibration” method to transform confinement into pressure. We focused on the effect of confinement on: (a) changes of electron distribution and localization within the K and L shells, (b) confinement-induced ionization pressure, (c) level crossing of electronic states, and (d) correlation energy. We found that contraction of valence and core-shells are not negligible and that the use of standard pseudopotentials might be not adequate to study solids under extreme pressures. The critical pressure at which atoms ionize follows a periodic trend, and it ranges from 28 GPa for Li to 10.8 TPa for Ne. In Li and Be, pressure induces mixing of the ground state configuration with excited states. At high pressure, the ground states of Li and Be become a doublet and a triplet with configurations 1s²2p and 1s²2s2p, respectively, which could change the chemistry of Be. Finally, it is observed that atoms with fewer electrons correlation increases, but for atoms with more electrons, the increasing of kinetic energy dominates over electron correlation.     

Ten-Electron Central Field Problem: An Inhomogeneous Electron Liquid

Abstract

Recent work has been carried out on the exchange energy density epsive;_x(r) of a ten-electron atomic ion in the (bare Coulomb) limit of large atomic number Z [Howard, I. A. et al (2000). Phys. Rev. A, 62, 062512]. This analytical study of epsive; x(r) was made possible by the existence of a closed form of the first-order (idempotent) density matrix (IDM).

Here, some generalizations are effected to a central potential energy V(r) which (a) localizes the ten electrons and (b) yields closed K and L shells for these ten electrons occupying the lowest eigenstates with spin compensation. In particular, it is shown that p-shell properties alone determine the IDM in this example of a confined inhomogeneous electron liquid.     

Soft Coulomb hole method applied to molecules

The soft Coulomb hole method introduces a perturbation operator, defined by ?e/r₁₂ to take into account electron correlation effects, where ω represents the width of the Coulomb hole. A new parametrization for the soft Coulomb hole operator is presented with the purpose of obtaining better molecular geometries than those resulting from Hartree–Fock calculations, as well as correlation energies. The 12 parameters included in ω were determined for a reference set of 12 molecules and applied to a large set of molecules (38 homo‐ and heteronuclear diatomic molecules, and 37 small and medium‐size molecules). For these systems, the optimized geometries were compared with experimental values; correlation energies were compared with results of the MP2, B3LYP, and Gaussian 3 approach. On average, molecular geometries are better than the Hartree–Fock values, and correlation energies yield results halfway between MP2 and B3LYP. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

NDDO MO Calculations

Siegbahn's potential model as extended by Ellison et al. is used with density matrix elements calculated by the NDDO/2 procedure, to correlate the K-shell binding energy shifts of C, N and O atoms in a few molecules containing only the first-row atoms. The correlation is not superior to that obtained with the CNDO/2 method when only the monopole term is retained in calculating the Madelung potential energy. However, the results are in excellent agreement with experiment when the two-parameters model including the dipole and quadrupole terms is used.     

Model universal coulomb hole function for many-electron systems

In the framework of the homogeneous electron gas theory we give a model function G_c of the Coulomb hole that can be considered as an approximate universal correlation function for many-electron systems. The function G_c reflects the right asymptotic behavior of the correlation function of an electron gas in high and low density limits and enables one to reproduce experimental correlation energies of a number of atoms of the first and second periods in a local density approximation with the relative error 0.3–4.2%. The estimate of contributions of electrons with parallel or antiparallel spins into correlation energy shows that in the domain of densities typical for atoms of the first and second periods, the Coulomb correlation of electrons with parallel spins is in high extent suppressed by the Fermi correlation.     

Pair Function and Structure Factor of an Interacting Electron Liquid

Abstract

Recent work on small angle scattering from liquid metals has caused renewed interest in the electron pair function in the uniform interacting electron liquid, jellium. Therefore we have re-examined this problem, starting from an analysis of the exchange hole, in which the only correlations are due to the Pauli Principle and solely therefore between parallel spin electrons. The pair function g(r) of noninteracting Fermions is expressed in terms of the density of the p-component in the free electron density matrix. This motivates the treatment of the Coulomb repulsion via a potential energy V(r) To close the theory, one must either invoke self-consistency to determine V(r), or relate it to the (direct) correlation function c(r) as in classical liquids. Both methods are briefly considered; the second has the advantage that here the collective plasma oscillations can be introduced through their zero-point energy.     

Shake-off effects on the production and decay of hollow ions

An improved form of the radiative-Auger-cascade model is presented in which the shake-off contribution is incorporated into the model in a mathematically consistent way, avoiding the problem of double counting. The higher charge state distribution found in the photoionization experiment of the 1s electron in Ne is shown to be predominantly due to the shake-off effect during the formation of the 1s hole, and not during the cascade decays as previously assumed. This shake-off contribution is estimated in the sudden approximation, in terms of overlaps between the neutral and singly ionized ions. An excellent agreement with experiment is obtained in the case of Ne⁺ with 1s hole. The details of the X-ray and Auger spectra are also predicted by the new model both for the Ne and Mg ions. The shake-off effect on the resonant processes in general is discussed.