First-principles study of ferroelectricity and isotope effects in H-bonded KH2PO4 crystals

By means of extensive first-principles calculations we studied the ferroelectric phase transition and the associated isotope effect in KH2PO4 (KDP). Our calculations revealed that the spontaneous polarization of the ferroelectric phase is due to electronic charge redistributions and ionic displacements which are a consequence of proton ordering, and not vice versa. The experimentally observed double-peaked proton distribution in the paraelectric phase cannot be explained by a dynamics of only protons. This requires, instead, collective displacements within clusters that include also the heavier ions. These tunneling clusters can explain the recent evidence of tunneling obtained from Compton scattering measurements. The sole effect of mass change upon deuteration is not sufficient to explain the huge isotope effect. Instead, we find that structural modifications deeply connected with the chemistry of the H bonds produce a feedback effect on tunneling that strongly enhances the phenomenon. The resulting influence of the geometric changes on the isotope effect agrees with experimental data from neutron scattering. Calculations under pressure allowed us to analyze the issue of universality in the disappearance of ferroelectricity upon compression. Compressing DKDP so that the distance between the two peaks in the deuteron distribution is the same as for protons in KDP, corresponds to a modification of the underlying double-well potential, which becomes 23 meV shallower. This energy difference is what is required to modify the O-O distance in such a way as to have the same distribution for protons and deuterons. At the high pressures required experimentally, the above feedback mechanism is crucial to explain the magnitude of the geometrical effect.

Direct Observation of strong coupling in a laser-shock compressed plasma

In this Letter we report on a near collective x-ray scattering experiment on shock-compressed targets. A highly coupled Al plasma was generated and probed by spectrally resolving an x-ray source forward scattered by the sample. A significant reduction in the intensity of the elastic scatter was observed, which we attribute to the formation of an incipient long-range order. This speculation is confirmed by x-ray scattering calculations accounting for both electron degeneracy and strong coupling effects. Measurements from rear side visible diagnostics are consistent with the plasma parameters inferred from x-ray scattering data. These results give the experimental evidence of the strongly coupled ionic dynamics in dense plasmas.

Dissociative electron attachment to the highly reactive difluoromethylene molecule–importance of CF2 for negative ion formation in fluorocarbon plasmas

Dissociative electron attachment to the highly reactive difluoromethylene molecule, CF2, produced in a C3F6/He microwave plasma and stepwise via the fast atom reaction CF3I+H?CF3+HI and CF3+H?CF2+HF, has been investigated. The upper limit for the cross section of formation of F- via dissociative electron attachment to CF2 is estimated to be 5×10-4?Å2. This value is four orders of magnitude smaller than the cross section previously predicted from scattering calculations. It is concluded that difluoromethylene plays a negligible role in negative ion formation in fluorocarbon plasmas.

High-resolution electron energy-loss spectroscopy of Ba Ti O 3∕ Sr Ti O 3 multilayers

The dielectric properties of BaTiO3 thin films and multilayers are different from bulk materials because of nanoscale dimensions, interfaces, and stress-strain conditions. In this study, BaTiO3/SrTiO3 multilayers deposited on SrTiO3 substrates by pulsed laser deposition have been investigated by high-energy-resolution electron energy-loss spectroscopy. The fine structures in the spectra are discussed in terms of crystal-field splitting and the internal strain. The crystal-field splitting of the BaTiO3 thin layer is found to be a little larger than that of bulk BaTiO3, which has been interpreted by the presence of the internal strain induced by the misfit at the interface. This finding is consistent with the lattice parameters of the BaTiO3 thin layer determined by the selected area diffraction pattern. The near-edge structure of the oxygen K edge in BaTiO3 thin layers and in bulk BaTiO3 are simulated by first-principle self-consistent full multiple-scattering calculations. The results of the simulations are in a good agreement with the experimental results. Moreover, the aggregation of oxygen vacancies at the rough BaTiO3/SrTiO3 interface is indicated by the increased [Ti]/[O] element ratio, which dominates the difference of dielectric properties between BaTiO3 layer and bulk materials.

The 2p interloper resonances in collisions

Ab initio electron scattering calculations using the R -matrix approach have been performed for within a three-state valence configuration-interaction model (VCI). The lowest three electronic target states ( , and the ) of this molecular nitrogen cation are included in the close-coupling method, with each state being represented by a valence CI approximation. From a detailed analysis of the resonance structure found in our work for the symmetries we find four prominent Rydberg series of the type , , , and a interloper resonance. This interloper molecular resonance associated with the B state of is seen to cause distortions of the resulting resonance spectra. A comparison of our total cross sections for the X - B transition shows excellent agreement with the available experimental data.

Positronium scattering by Ne, Ar, Kr and Xe in the frozen target approximation

A full-electron coupled-state treatment of positronium (Ps)- inert gas scattering is developed within the context of the frozen target approximation. Calculations are performed for Ps(Is) scattering by Ne and Ar in the impact energy range 0-40 eV using coupled pseudostate expansions consisting of nine and 22 Ps states. The purpose of the pseudostates is primarily to represent ionization of the Ps which is found to be a major process at the higher energies. First Born estimates of target excitation are used to complement the frozen target results. The available experimental data are discussed in detail. It is pointed out that the very low energy measurements (less than or equal to2 eV) correspond to the momentum transfer cross section sigma(mom) and not to the elastic cross section sigma(el). Calculation shows that sigma(mom), and sigma(el) diverge very rapidly with increasing energy and consequently comparisons of the low-energy data with ITel can be very misleading. Agreement between the calculations and the low-energy measurements of anion as well;as higher energy (greater than or equal to15 eV) beam measurements of the total cross section, is less than satisfactory. Results for Ps(1s) scattering by Kr and Xe in the static-exchange approximation are also presented.

Positronium scattering by atomic hydrogen with inclusion of target excitation channels

Calculations are reported for positronium (Ps) scattering by atomic hydrogen (H) in the energy range 0-6.5 eV in a coupled- pseudostate approximation in which excitation and ionization channels of both the Ps and the H are taken into account. The approximation contains an accurate representation of the van der Waals coefficient. Results are presented for phase shifts, scattering lengths, effective ranges, and various cross sections including partial wave, total, and ortho-para conversion cross sections. An analysis of the possible spin transitions is provided and the energy of the positronium hydride (PsH) bound state is determined. Substantial differences are found from earlier work within the frozen target approximation, now clearly confirming the importance of target excitation channels. Good agreement is obtained with recent calculations of S-wave phase shifts and scattering lengths using the stabilization method. Convergence to the exact binding energy for PsH appears to be slow. Resonances corresponding to unstable states of the positron orbiting H- are seen in the electronic spin singlet partial waves. The importance of the H- formation channel is discussed.

Positron scattering by the negative hydrogen ion

Results are presented for e(+) scattering by H- in the impact energy range 0less than or equal toE(0)less than or equal to10 eV. These include integrated cross sections for Ps formation in the 1s, 2s, and 2p states, as well as in an aggregate of states with ngreater than or equal to3, and for direct ionization. Differential cross sections for Ps formation in the 1s, 2s, and 2p states are also exhibited. The calculations are based on a coupled pseudostate approach employing 19 Ps pseudostates centered on the e(+). It is found that Ps formation in the 2p state dominates that in the 1s or 2s states below 8 eV, that formation in states with ngreater than or equal to3 exceeds the sum of the n=1 and n=2 cross sections above 2.5 eV, and that direct ionization outstrips total Ps formation above 6.3 eV. The threshold law (E-0-->0) for exothermic Ps formation, which includes the cases Ps(1s), Ps(2s), and Ps(2p), is shown to be 1/E-0.

Positronium scattering by lithium

We report cross sections for Ps(1s)-Li(2s) scattering in the energy range up to 30 eV. The calculations have been carried out in a coupled state approximation. The Ps states consist of both eigenstates and pseudostates. the latter to allow for ionization of the Ps. The atom is treated as a frozen core represented by it model potential which supports the valence orbitals. The coupled state expansion includes only the 2s and 2p states of the atom as well as in unphysical Is state which exists in the model potential. The inclusion of this Is state is necessary in order to avoid pronounced false pseudostructure. Results are presented for excitation and ionization of the Ps as well as collisions in which the Ps(1s) remains unchanged. These results also differentiate between the case where the Li(2s) remains unexcited and where it is excited to the 2p level. (c) 2005 Published by Elsevier B.V.

R-matrix theory of electron molecule scattering

This paper presents an overview of R-matrix theory of electron scattering by diatomic and polyatomic molecules. The paper commences with a detailed discussion of the fixed-nuclei approximation which in recent years has been used as the basis of the most accurate ab initio calculations. This discussion includes an overview of the computer codes which enable electron collisions with both diatomic and polyatomic molecules to be calculated. Nuclear motion including rotational and vibrational excitation and dissociation is then discussed. In non-resonant energy regions, or when the scattered electron energy is not close to thresholds, the adiabatic-nuclei approximation can be successfully used. However, when these conditions are not applicable, non-adiabatic R-matrix theory must be used and a detailed discussion of this theory is given. Finally, recent applications of the theory to treat electron scattering by polyatomic molecules are reviewed and a detailed comparison of R-matrix calculations and experimental measurements for water is presented.

Angular distribution for the elastic scattering of electrons from Ar+(3s^2 3p^5 ^2P) above the first inelastic threshold

The measured angular differential cross section (DCS) for the elastic scattering of electrons from Ar+(3s2 3p5 2P) at the collision energy of 16 eV is presented. By solving the Hartree-Fock equations, we calculate the corresponding theoretical DCS including the coupling between the orbital angular momenta and spin of the incident electron and those of the target ion and also relaxation effects. Since the collision energy is above one inelastic threshold for the transition 3s2 3p5 2P–3s 3p6 2S, we consider the effects on the DCS of inelastic absorption processes and elastic resonances. The measurements deviate significantly from the Rutherford cross section over the full angular range observed, especially in the region of a deep minimum centered at approximately 75°. Our theory and an uncoupled, unrelaxed method using a local, spherically symmetric potential by Manson [Phys. Rev. 182, 97 (1969)] both reproduce the overall shape of the measured DCS, although the coupled Hartree-Fock approach describes the depth of the minimum more accurately. The minimum is shallower in the present theory owing to our lower average value for the d-wave non-Coulomb phase shift s2, which is due to the high sensitivity of s2 to the different scattering potentials used in the two models. The present measurements and calculations therefore show the importance of including coupling and relaxation effects when accurately modeling electron-ion collisions. The phase shifts obtained by fitting to the measurements are compared with the values of Manson and the present method.

Convergence of partial-wave expansions for energies, scattering amplitudes and positron annihilation rates

We use many-body theory to find the asymptotic behaviour of second-order correlation corrections to the energies and positron annihilation rates in many- electron systems with respect to the angular momenta l of the single-particle orbitals included. The energy corrections decrease as 1/(l+1/2)4, in agreement with the result of Schwartz, whereas the positron annihilation rate has a slower 1/(l+1/2)2 convergence rate. We illustrate these results by numerical calculations of the energies of Ne and Kr and by examining results from extensive con?guration-interaction calculations of PsH binding and annihilation.

Extracting S-matrix poles for resonances from numerical scattering data: Type-II Pade reconstruction

We present a FORTRAN 77 code for evaluation of resonance pole positions and residues of a numerical scattering matrix element in the complex energy (CE) as well as in the complex angular momentum (CAM) planes. Analytical continuation of the S-matrix element is performed by constructing a type-II Pade approximant from given physical values (Bessis et al. (1994) [421: Vrinceanu et al. (2000) [24]; Sokolovski and Msezane (2004) [23]). The algorithm involves iterative 'preconditioning' of the numerical data by extracting its rapidly oscillating potential phase component. The code has the capability of adding non-analytical noise to the numerical data in order to select 'true' physical poles, investigate their stability and evaluate the accuracy of the reconstruction. It has an option of employing multiple-precision (MPFUN) package (Bailey (1993) [451) developed by D.H. Bailey wherever double precision calculations fail due to a large number of input partial waves (energies) involved. The code has been successfully tested on several models, as well as the F + H-2 -> HE + H, F + HD : HE + D, Cl + HCI CIH + Cl and H + D-2 -> HD + D reactions. Some detailed examples are given in the text.

B-spline methods in R-matrix theory for scattering in two-electron systems

The use of B-spline basis sets in R-matrix theory for scattering processes has been investigated. In the present approach a B-spline basis is used for the description of the inner region, which is matched to the physical outgoing wavefunctions by the R-matrix. Using B-splines, continuum basis functions can be determined easily, while pseudostates can be included naturally. The accuracy for low-energy scattering processes is demonstrated by calculating inelastic scattering cross sections for e colliding on H. Very good agreement with other calculations has been obtained. Further extensions of the codes to quasi two-electron systems and general atoms are discussed as well as the application to (multi) photoionization.