Relativistic density functional investigation of UX6（X=F,Cl,Br and I）

The molecular structures and the vibrational frequencies of uranium hexahalides UX 6(X=F,Cl,Br and I) molecules are investigated by using local density approximation(LDA) and generalised gradient approximation(GGA) functions(BP,BLYP and RPBE) in combination with two different relativistic methods(scalar and scalar+spin-orbit relativistic effects).The calculated results show that the differences are trivial between scalar and scalar+spin-orbit relativistic methods.The vibrational frequencies are also compared with existing experimental values,and overall,the RPBE approach gives the smallest error.The bond dissociation energies(BDEs) of UX 6 are computed by using the RPBE function,thereby obtaining exact vibrational frequencies.In addition,the calculated magnitudes of the spin-orbit effect on the BDE of UX 6(X=F,Cl,Br,and I) are found to be approximately-0.3198,-0.3218,-0.3609 and-0.4415 eV,respectively.     

Probing the basis set limit for thermochemical contributions of inner-shell correlation: balance of core-core and core-valence contributions*

ABSTRACT

The inner-shell correlation contributions to the total atomisation energies of the W4-17 computational thermochemistry benchmark have been determined at the CCSD(T) level near the basis set limit using several families of core correlation basis sets, such as aug-cc-pCVnZ (n?=?3–6), aug-cc-pwCVnZ (n?=?3–5) and nZaPa-CV (n?=?3–5). The three families of basis sets agree very well with each other (0.01?kcal/mol RMS) when extrapolating from the two largest available n: however, there are considerable differences in convergence behaviour for the smaller basis sets. nZaPa-CV is superior for the core-core term and awCVnZ for the core-valence term. While the aug-cc-pwCV(T+d)Z basis set of Yockel and Wilson is superior to aug-cc-pwCVTZ, further extension of this family proved unproductive. The best compromise between accuracy and computational cost, in the context of high-accuracy computational thermochemistry methods, is CCSD(T)/awCV{T,Q}Z, where the {T,Q} notation stands for extrapolation from the awCVTZ and awCVQZ basis set pair. For lower-cost calculations, we recommend a previously proposed combination of CCSD-F12b/cc-pCVTZ-F12 and CCSD(T)/pwCVTZ(no f). While in first-row molecules core-valence correlation on average accounts for over 90% of the inner-shell contribution, in second-row molecules core-core contributions may become important, particularly in systems like P₄ and S₄ with multiple adjacent second-row atoms.     

Consistent treatment of relativistic corrections in deuteron photodisintegration in a one-pion-exchange model

Using a one-pion-exchange model for the nucleon-nucleon interaction the relativistic corrections to potential and to the electromagnetic operators are derived in a power expansion of (p/M). All corrections up to the order (p/M)³ are consistently included. Numerical results are shown for differential cross section and polarization observables for deuteron photodisintegration. A sizeable influence of relativistic effects on some observables is found even at low energies. A comparison of our operators with the expressions of other authors is given.Supported by Deutsche Forschungsgemeinschaft (SFB 201)     

Relativistic energies and transition probabilities for some highly excited levels in singly ionized indium

For some excited levels (n?8), the energies, wavelengths, oscillator strengths and transition probabilities calculations in singly ionized indium have been calculated within the framework of multiconfiguration Hartree-Fock approximation with relativistic corrections (Breit-Pauli Hamiltonian). The wavefunctions and some relativistic corrections have been obtained using MCHF-BP atomic package. Comparisons with other calculations and experiments are presented.     

Ab initio potential energy curve for the helium atom pair and thermophysical properties of dilute helium gas. I. Helium–helium interatomic potential

A helium–helium interatomic potential energy curve was determined from quantum-mechanical ab initio calculations. Very large atom-centred basis sets including a newly developed d-aug-cc-pV8Z basis set supplemented with bond functions and ab initio methods up to full CI were applied. The aug-cc-pV7Z basis set of Gdanitz (J. Chem. Phys. 113, 5145 (2000)) was modified to be more consistent with the aug-cc-pV5Z and aug-cc-pV6Z basis sets. The diagonal Born–Oppenheimer corrections as well as corrections for relativistic effects were also calculated. A new analytical representation of the interatomic potential energy was fitted to the ab initio calculated values. In a following paper this potential model will be used in the framework of quantum-statistical mechanics and of the corresponding kinetic theory to calculate the most important thermophysical properties of helium governed by two-body and three-body interactions.     

Theoretical study of LiCl− and LiBr− molecular ions

The molecular structures and spectroscopic constants of the ground electronic states of LiCl^? and LiBr^? are investigated with the coupled-cluster method. To improve the accuracy of our calculations, we have employed the extrapolation schemes as well as corrections of the core–valence correlation and scalar relativistic effect. The equilibrium parameters, potential energy curves, force constants, vibrational energy levels and spectroscopic parameters of both molecular ions are derived, in which those of LiBr^? are reported for the first time. The electron affinities and vertical detachment energies of neutral and anionic LiCl and LiBr are also evaluated.     

Scalar Soliton in Newtonian Gravity Modelling Dark Matter Halos

Within standard Newtonian gravity, galactic dark matter is modelled by a scalar field in order to effectively modify Kepler's law. In particular, we show that a solvable toy model with a self-interaction U() borrowed from non-topological solitons produces already qualitatively correct rotation curves. Although relativistic effects in the halo are very small, we indicate corrections arising from the general relativistic formulation.     

Study of photon-induced L3 vacancy alignment for elements La to U

Alignment of photon-induced L₃ vacancies is studied in rare earth and highZ elements at energies of experimental interest, near thresholds to 60 keV, under nonrelativistic dipole approximation. Numerical calculations of the matrix element are undertaken to produce theoretical data for comparison with the experimental findings. The A₂ values being s>0.1 at photoelectron energies <20 keV are certainly higher than 5–8% uncertainties quoted in experimental results. Present findings are from a very basic model, hydrogen-like and can further be treated as reference to observe the impact of screening, relativistic, multipole and retardation corrections to the model     

Weak point disorder in strongly fluctuating flux-line liquids

We consider the effect of weak uncorrelated quenched disorder (point defects) on a strongly fluctuating flux-line liquid. We use a hydrodynamic model which is based on mapping the flux-line system onto a quantum liquid ofrelativistic charged bosons in 2 + 1 dimensions [P Benetatos and M C Marchetti,Phys. Rev. B64, 054518 (2001)]. In this model, flux lines are allowed to be arbitrarily curved and can even form closed loops. Point defects can be scalar or polar. In the latter case, the direction of their dipole moments can be random or correlated. Within the Gaussian approximation of our hydrodynamic model, we calculate disorder-induced corrections to the correlation functions of the flux-line fields and the elastic moduli of the flux-line liquid. We find that scalar disorder enhances loop nucleation, and polar (magnetic) defects decrease the tilt modulus.     

Nuclear structure effects in parity non-conservation in heavy ions

We calculate the binding energy, charge radii in ¹²⁹Ba-¹⁴³Ba and ²¹⁴Ra-²²⁸Ra using the relativistic mean field theory which includes scalar and vector mesons. We then evaluate the nuclear structure corrections to the weak charges for a series of these isotopes using different parameters and estimate their uncertainty in the framework of this model. Our results will have important implication for the ongoing and planned parity nonconservation experiments and atomic structure calculations on Ba⁺ and Ra⁺.     

Testing atomic structure theories with high accuracy mass measurements on highly charged ions

The mass of a highly charged ion is the sum of the mass of the nucleus, the mass of the electrons and the electronic binding energies. High accuracy mass measurements on highly charged ions in a sequence of different charge states yield informations on atomic binding energies, i.e., the ionisation potentials. In our contribution we discuss the possibility of determining atomic binding energies of highly charged ions to better than 20 eV via cyclotron frequency measurements in a Penning trap. At this level of accuracy different contributions to the binding energies, like relativistic corrections, Breit corrections and QED corrections, can be measured. This revised version was published online in August 2006 with corrections to the Cover Date.     

Corrections to the Casimir–Polder potential arising from electric octupole coupling

ABSTRACT

Molecular QED theory is employed to derive a generalised formula for the dispersion potential between two molecules with mixed electric multipole polarisability tensors of arbitrary order at each centre. This expression is used to readily extract the pair energy shift between an electric dipole polarisable molecule and a mixed electric dipole–octupole polarisable one, and that between two mixed electric dipole–octupole polarisable species. This is done to see whether these interaction energies give rise to higher-order corrections to the Casimir–Polder potential, as was found in the previously calculated case of the dispersion energy shift between an electric dipole polarisable molecule and an electric octupole polarisable one. Interestingly, for orientationally averaged species, both of the computed interaction energies are independent of the octupole weight-3 term, are retarded, and may be interpreted as higher-order corrections in the fine structure constant to the leading dipole–dipole dispersion potential.     

原子核的有限体积效应对高离化态离子能级和波函数的影响

在相对论理论框架下,分别在点电荷和两参数Fermi核模型近似下计算了高离化态类氢离子（Z=80—112）n=1—3壳层的波函数和能级. 分析了核有限体积效应对它们的影响. 在此基础上,给出了核有限体积效应对原子能级的修正公式. 同时,还进一步讨论了相对论效应和核有限体积效应之间的相互影响,发现对高Z元素相对论效应与核有限体积效应之间有很强的耦合. 关键词： 原子核有限体积效应 高离化态离子 相对论效应     

Symmetries of the Relativistic Two-Particle Model with Scalar-Vector Interaction

Abstract

A relativistic two-particle model with superposition of time-asymmetric scalar and vector interactions is proposed and its symmetries are considered. It is shown that first integrals of motion satisfy nonlinear Poisson-bracket relations which include the Poincaré algebra and one of the algebras so(1,3), so(4) or e(3).     

Theoretical characterization of the HSOH,H2SO and H2OS isomers

The HSOH, H₂SO and H₂OS isomers have been investigated employing the CCSD(T) methodology and the cc-pV(X + d)Z X = 3,4,5,6 basis sets. The anharmonic force fields have been calculated to predict the fundamental vibrational frequencies, rotational constants, vibration–rotation corrections, anharmonic corrections to zero-point energies, and structural parameters. In addition to this, a spectroscopic characterization of the deuterated isomers D₂SO and D₂OS was performed. At the CCSD(T)/CBS limit and including corrections for scalar relativistic, spin orbit and core-valence correlation effects, the estimated enthalpies of formation are ?28.1 ± 1, ?12.3 ± 1, and 10.1 ± 1 kcal/mol for HSOH, H₂SO and H₂OS, respectively. Finally, we discuss the problems faced during the extrapolation to the CBS limit of the properties investigated.     

Elastic scattering of e∓ by Na atoms

ABSTRACT

The differential, integrated elastic, momentum transfer, viscosity and total cross-sections along with Sherman function for the elastic scattering of electrons and positrons by sodium atoms have been calculated within the framework of complex projectile–atom optical potential model at the impact energies 0.1 ≤ E_i ≤ 10⁴ eV for both the projectiles. The relativistic Dirac partial wave techniques, with accurate analytical charge densities, are used to obtain the scattering amplitudes. The present results produce satisfactory agreement with the experimental measurements and other theoretical calculations available in the literature.     

探测二茂铁外价轨道(e,2e)反应中的扭曲波效应

利用第三代高效率电子动量谱仪,分别在600和1500 eV两种不同入射电子能量下获得了二茂铁(ferrocene)分子外价轨道的电离能谱和电子动量谱的相关实验结果.并利用非相对论与标量相对论密度泛函方法计算出了二茂铁的重叠型和交错型两种不同构象的理论动量谱.两种构象的外价轨道一一对应,理论电子动量谱基本一样.对二茂铁的外价轨道,在低动量区观测到了强烈的扭曲波效应,这与这些轨道主要由铁原子的3d轨道构成有关.通过相对论和非相对论计算结果的比较,表明相对论效应对于二茂铁的外轨道动量分布几乎没有影响. 关键词： 二茂铁分子 电子动量谱 相对论效应 扭曲波效应     

Total electron ionization cross-sections for molecules of astrochemical interest

ABSTRACT

We describe a newly upgraded instrument for measuring absolute total electron ionization cross-sections over the energy range from 0 to 300?eV, and present cross-sections for nine previously unstudied molecules, as well as several small molecules for which comparison data is available. The measured cross-sections are compared with the predictions of the BEB model, and show reasonable agreement with the model, albeit peaking at higher electron energies than predicted by the model. We show that the maxima in the cross-sections follow an additivity model, such that the molecular cross-sections can be expressed as a sum over contributions from the constituent atoms. These contributions have been determined from a global fit to the data for all molecules studied, and allow maximum cross-sections to be predicted for molecules that have not been studied to date. We demonstrate the expected correlation between the maximum ionization cross-section and the molecular polarisability, and show that the atomic contributions to the cross-section show a similar dependence on the atomic polarisability. The observed correlation can be used as an alternative method for predicting unknown maximum cross-sections.     

Accurate ab initio anharmonic force field and heat of formation for silane

From large basis set coupled cluster calculations and a minor empirical adjustment, an anharmonic force field for silane has been derived that is consistently of spectroscopic quality (±1 cm^?1 on vibrational fundamentals) for all isotopomers of silane studied. Inner-shell polarization functions have an appreciable effect on computed properties and even on anharmonic corrections. From large basis set coupled cluster calculations and extrapolations to the infinite-basis set limit, we obtain TAE₀ = 303.80 ± 0.18 kcal mol^?1, which includes an anharmonic zero-point energy (19.59 kcal mol^?1), inner-shell correlation (—0.36 kcal mol^?1), scalar relativistic corrections (— 0.70 kcal mol^?1) and atomic spin-orbit corrections (—0.43 kcal mol^?1). In combination with the recently revised ΔH ^o _{f, o}[Si(g)], we obtain ΔH ^o _f.o[SiH₄(g)] = 9.9 ± 0.4 kcal mol^?1 in between the two established experimental values.     

Classical and quantum scattering by a Coulomb potential

For relativistic energies the small-angle classical cross section for scattering on a Coulomb potential agrees with the first Born approximation for quantum cross section for scalar particle only in the leading term. The disagreement in other terms can be avoided if the sum of all corrections to the first Born approximation for large enough Coulomb charge contains the classical terms which are independent of that charge. The difference in classical and quantum cross sections may be partly attributed to the fact that the relativistic quantum particle can rush through the field without interaction. We expect that smaller impact parameters and spin facilitate this effect. The text was submitted by the authors in English.