A theory of vibrational frequency shifts revisited: application to dimers of LiH with the inert gases He,Ne, Ar and Kr

The objective of this paper is to contribute towards an understanding of the anomalous blue vibrational shifts that have been observed on forming some hydrogen bonds. It is shown that linear complexes of the LiH molecule with an inert gas atom Rg exhibit red or blue shifts of the LiH vibrational frequency depending upon whether Rg is attached to the Li or the H atom.

The shifts in the frequency of the Li–H vibration on forming the weakly bound linear complexes Li–H…Rg and H–Li…Rg (Rg?=?He, Ne, Ar, Kr) were determined by ab initio computations at the MP2/6-311++G(2d,?2p) level of theory. These frequency shifts were found to be in good agreement with predictions from a model based on perturbation theory and involving first and second derivatives U′ and U′′ of the interaction energy with respect to displacement of the Li–H bond length from its equilibrium value in the isolated molecule. Concentration of the Li–H vibrational motion in the light H atom causes U′ and U′′ to be dominated by repulsion in Li–H…Rg and by attraction in H–Li…Rg, producing blue and red shifts, respectively. The bond length changes on complexation are well predicted by U′.     

Auger decay and the direct double ionization probability of a 2p inner-shell hole in a singly charged Ar+ ion

We have performed multi-component full-configuration interaction calculations to investigate the nature of chemical bonding of [LiH;e⁺] at the small and large internuclear distance. We discuss the importance of geometrical changes in positronic compounds induced by a positron attachment in terms of the virial theorem, with a comparison of the adiabatic- and vertical-positron affinity (PA). The systematic improvement of the PA values achieved by optimisation of (i) the molecular geometry and (ii) the positronic basis centre is also discussed. The stable dissociation channel of [LiH;e⁺] is compared with the ionic- and neutral-dissociation channels of its parent molecule LiH through the analysis of the potential energy curve and the electronic and positronic densities. The vertical PA as a function of is also presented, which is the difference between the potential energy curve of the parent molecule (LiH → Li + H) and its positronic compound ([LiH; e⁺] → Li + [H; e⁺]). Unlike the preceding study of [M. Mella et al., J. Chem. Phys. 113, 6154 (2000)], it took more than bohr to converge the vertical PA due to the long-range ionic bonding interaction.     

Enhanced cooling of hydrogen atoms by lithium atoms

We present calculated scattering lengths for collisions between various isotopic forms of lithium and hydrogen atoms interacting via singlet and triplet molecular states of LiH. We demonstrate that one bound triplet level is supported for each isotopomer 7LiH, 6LiH, 7LiD, and 6LiD. We obtain large calculated triplet scattering lengths that are stable against uncertainties in the potential. We present elastic and momentum transfer cross sections, and the corresponding rate coefficients, for hydrogen atoms colliding with 7Li atoms. We suggest that enhanced cooling of trapped atomic hydrogen by 7Li atoms is feasible.     

Mössbauer spectra obtained using β − γ coincidence method after 57Mn implantation into LiH and LiD

Highly energetic ⁵⁷Mn (T_1/2 = 1.45 m) was generated by nuclear projectile fragmentation in a heavy-ion accelerator, and implanted into lithium hydride (LiH) and lithium deuteride (LiD) at 578 K. Mössbauer spectroscopy with β ? γ coincidence detection was then carried out on the ⁵⁷Fe obtained from β^?decay of the ⁵⁷Mn to study the time dependence of the site distributions and coordination environments of dilute Fe atoms implanted in the LiH and LiD. The results suggest that the Fe atoms can substitute for either the Li and H or D atoms within 100 ns. Additionally, the displacement behavior of the substitutional ⁵⁷Fe atoms on the lattice sites is discussed.     

Excitation functions of191+193Ir,197Au(6Li,xn+yp) compound nuclear reactions at ELi=48–156 MeV

Excitation functions of the compound nuclear reactions^191+193Ir,¹⁹⁷Au(⁶Li,xn+yp) forx =3–13 andy=0–2 have been investigated by means of in-beamγ-ray spectroscopy at the 156 MeV⁶Li beam of the Karlsruhe Isochronous Cyclotron. The beam energy has been varied in the range of 48 to 156 MeV in steps of about 10 MeV by Be-absorber foils in the external beam line. Absolute cross sections have been determined by normalizing the measuredγ-ray intensities to the production cross sections ofK- X-rays in the target. The experimental excitation functions are discussed on the basis of predictions of the preequilibrium (hybrid) model. While in most cases the theoretical calculations fairly well reproduce energy position and shapes of the curves, strong discrepancies in the absolute scale of the cross sections are observed. The theoretical predictions overestimate the (⁶Li,xn) cross sections by a factor of about 6. Conspicuous anomalies have been detected when comparing the (⁶Li, xn+1(2)p) reactions with (⁶Li,xn) reactions. The reactions with emission of one or two protons are considerably enhanced. The discrepancies and anomalies observed are tentatively explained by the influence of direct reaction channels as the⁶Li break-up, which experimentally proved to be the dominant contribution to the total reaction cross section. The enhancement of the reactions with emission of protons may be a consequence of transfer reactions into highly excited states combined with compound nucleus formation thus implying a cluster effect in preequilibrium emission process.     

Prospects for sympathetic cooling of molecules in electrostatic, ac and microwave traps

We consider how trapped molecules can be sympathetically cooled by ultracold atoms. As a prototypical system, we study LiH molecules co-trapped with ultracold Li atoms. We calculate the elastic and inelastic collision cross sections of ⁷LiH + ⁷Li with the molecules initially in the ground state and in the first rotationally excited state. We then use these cross sections to simulate sympathetic cooling in a static electric trap, an ac electric trap, and a microwave trap. In the static trap we find that inelastic losses are too great for cooling to be feasible for this system. The ac and microwave traps confine ground-state molecules, and so inelastic losses are suppressed. However, collisions in the ac trap can take molecules from stable trajectories to unstable ones and so sympathetic cooling is accompanied by trap loss. In the microwave trap there are no such losses and sympathetic cooling should be possible.     

In-beam M?ssbauer spectroscopy of 57 Mn implanted into lithium hydride

We measured the temperature dependence of ⁵⁷Fe M?ssbauer spectra obtained after ⁵⁷Mn implantation into polycrystalline LiH with an extremely low implantation dose. Density functional calculations suggested that the Fe atoms were predominantly implanted into both Li and H substitutional sites of the LiH crystal.     

Results of the search forK-series X-rays from kaonic hydrogen

The X-ray spectrum associated withK ^? stopping in liquid hydrogen was measured with high resolution Si(Li) detectors. The totalK X-ray yield is not larger than 8×10^?4 per stoppedK ^? assuming no line broadening. A weak line pattern was found, which was tentatively ascribed to theK ^? HK-series X-rays. The shift and width of the 1s level, deduced from this pattern, are ε_1s =+270±80 eV andΓ=560±260 eV, respectively.     

Studies of Li intercalation of hydrogenated graphene on SiC(0001)

The effects of Li deposition on hydrogenated bilayer graphene on SiC(0001) samples, i.e. on quasi-freestanding bilayer graphene samples, are studied using low energy electron microscopy, micro-low-energy electron diffraction and photoelectron spectroscopy. After deposition, some Li atoms form islands on the surface creating defects that are observed to disappear after annealing. Some other Li atoms are found to penetrate through the bilayer graphene sample and into the interface where H already resides. This is revealed by the existence of shifted components, related to H–SiC and Li–SiC bonding, in recorded core level spectra. The Dirac point is found to exhibit a rigid shift to about 1.25 eV below the Fermi level, indicating strong electron doping of the graphene by the deposited Li. After annealing the sample at 300–400 °C formation of LiH at the interface is suggested from the observed change of the dipole layer at the interface. Annealing at 600 °C or higher removes both Li and H from the sample and a monolayer graphene sample is re-established. The Li thus promotes the removal of H from the interface at a considerably lower temperature than after pure H intercalation.     

Variation of enhancement effect of Coster-Kronig transition of L3 X-Rays of Ba, La and Ce compounds

The Coster-Kronig (CK) enhancement effect was measured for L₃ subshell X-rays using the experimental Lα X-ray production cross-section, the fraction of Lα X-rays, L₃ subshell fluorescence yields and L₃ subshell photoionisation cross-section. The samples were excited by gamma-rays with 59.5 keV energy from a 75 mCi radioisotope source and L X-rays emitted from samples were counted by a Si(Li) detector with resolution 155 eV at 5.96 keV. Variation of enhancement effect of CK transition of L₃ X-rays of La and Ce compounds was measured to be more than that of Ba. Ba has a partially filled 6s orbital whereas La and Ce have partially filled 5d and 4f orbitals, respectively.     

Inner-shell ionization created by fluorine ions in nearly symmetric collisions

We have measured projectile and target X-ray cross sections for F + Si, S, Ar and Kr collisions at projectile energies from 1 to 25 MeV. The experiments were performed under single collision conditions using a differentially pumped gas target. X-rays were measured by a Si(Li) detector and a proportional counter. The experimental cross sections are compared to predictions of theoretical models for direct and quasi-molecular ionization. Effects of multiple ionization that influence theK-shell fluorescence yields were examined using experimental information from line energy shifts and intensity ratios.     

LiH电子结构和物态方程与离子半径比

 本文给出了用LMTO能带方法计算的离子晶体LiH的不同WS球半径比的计算结果。其压缩比σ=1.0~2.5。在电子带结构、电子占据数及零温物态方程等方面进行了比较。比较结果表明：二元化合物的原子半径比不同对计算的电子带结构及电子占据数有一定的影响，但对晶体的整体性质如物态方程、相变等影响不大。在高压情形下，这个影响减弱。     

Ab-initio nonrelativistic and relativistic Hartree-Fock calculations for both closed- and open-shell molecules using GTO basis

Computer programs forab-initio Hartree-Fock and Dirac-Hartree-Fock calculations on closed- and open-shell atoms and molecules have been indigenously developed. Sample results of high quality are given for Li, Be, LiH and Be₂. As a byproduct of these calculations the importance of considering relativistic effects in the investigation of the elusive bound-state structure of Be₂ is clearly indicated.     

Intrinsic ultraviolet luminescence of LiB<Subscript>3</Subscript>O<Subscript>5</Subscript> single crystals under inner-shell excitation

Ultraviolet photoluminescence (PL) of LiB₃O₅ (LBO) crystals has been studied under selective excitation by photons in the vacuum ultraviolet and ultrasoft x-ray regions, including the K-absorption edges of the Li and B cations and O anion. Radiative recombination of electron-hole pairs was established to be the main channel of the intrinsic PL excitation at 4.2 eV. Features were observed in the PL excitation spectra near the lithium and boron K-absorption edges originating from excitation of the cation 1s core excitons. Experimental evidence of the multiplication of Li 1s excitons in LBO was obtained. It is shown that excitation of the O 1s core excitons does not affect the PL yield noticeably. The differences in the appearance of the Li, B, and O 1s excitons in the excitation spectra of the LBO ultraviolet PL are discussed.     

Isotope selective laser enhancement of the Li+H2 reaction

The enhancement of the Li+H₂LiH+H reaction due to laser excitation of the Li atom to the2p state has been investigated using absorption techniques. Using a rate equation model we obtain from our data a reaction cross-section [Li(2p)+H₂LiH+H]=(0.10±0.03)Ų at 515°C. By selectively exciting one Li isotope the reaction is made isotope selective, suggesting an efficient means of isotope separation.     

Ab initio electronic, dynamic, and thermodynamic properties of isotopic lithium hydrides (LiH, LiD, LiT, LiH, LiD, and LiT)

The structural, dielectric, lattice-dynamical, and thermodynamical properties of isotopic lithium hydrides (⁶LiH, ⁶LiD, ⁶LiT, ⁷LiH, ⁷LiD, and ⁷LiT) were investigated within density-functional theory. The atomic structure was fully relaxed and the structural parameters were found to differ by less than 2% from the experimental data. The associated electronic band structure and density of states were also presented. A linear-response approach to the density-functional perturbation theory was employed to work out the Born effective charges, dielectric tensors and phonon frequencies, and thermodynamic properties. The compounds with the heavier Li isotope or H isotope have the lower phonon frequencies; ⁶LiT is more stable than ⁷LiT, ⁶LiD, ⁷LiD, ⁶LiH, and ⁷LiH in the temperature range 0-2700 K. These properties of LiT were predicted for the first time. The results were discussed in terms of the isotope effects on phonon dispersion curves and thermodynamic properties.     

Auger transitions initiated from singly and doubly ionized states in Li metal

Major events in Auger spectra from Li surfaces containing both Na and K have been identified. Li Auger transitions initiated from both singly and doubly ionized K shells of Li have been observed. However, no higher energy satellite corresponding to the coupling of the energy of a plasmon decay with that of the Li K VV Auger electrons was detected.     

Accurate calculation of the scattering length for the cooling of hydrogen atoms by lithium atoms

An improved ab initio calculation has been performed for the potential for the LiH a ³Σ⁺ state, using two very large basis sets. The Basis Set Superposition Error (BSSE) correction has been determined for both basis sets and the non-Born-Oppenheimer correction estimated to be negligible. The best potential is approximately 10% deeper than the previous estimate. Vibrational energies and scattering lengths have been calculated for ^6,7LiH(D) with both potentials, with and without the BSSE correction, and also with an estimated potential expected to bracket the true potential. The ⁷LiH scattering length is estimated to be (45 ± 4)a₀ and hence the low-energy cross-section in the best a ³Σ⁺ potential is about half that calculated previously. Enhanced cooling by ⁷Li of trapped H atoms remains feasible. Received 30 April 2001     

Evaluation of Expansion Coefficients from Optimal Fitting Parameters for the Analysis of Spectra of Diatomic Molecules and an Application to LiH

To evaluate individual expansion coefficients composing fitting parameters of the Born-Oppenheimer corrections to Dunham's coefficients Y(ij) that have been given analytically with the Delta(B) and Delta(omega) formalism, we examined the consistency of analytic expressions for those corrections with Watson's assertion of the experimental inseparability of nonadiabatic corrections Q(a, b)(r) for a molecule AB. Derived analytic expressions in terms of optimal fitting parameters for the corrections are essential to evaluate individual expansion coefficients. These expressions also reveal redundancies between empirical correction parameters Delta(ij). A method of evaluating nonadiabatic vibrational corrections Q(a, b)(r) and adiabatic corrections S(a, b)(r) separately consistent with Watson's assertion of inseparability is presented and is applied to an analysis of spectral data of LiH. Functions Q(a, b) and S(a, b) for LiH are thus successfully evaluated; S(H, Li)(r) values agree well with those predicted simply by wobble-stretch theory. Experimental values for optimal fitting parameters r(H)(1q) and r(H)(2q) are nearly equal to those of r(Li)(1q) and r(Li)(2q), respectively, in agreement with a theoretical relation r(a)(iq)=r(b)(iq). Copyright 2001 Academic Press.     

The d(7Li,p)8Li cross section near E cm = 0.61 MeV

The absolute cross section σ of the d(⁷Li, p)⁸Li reaction near the E_cm = 0.61 MeV resonance has been measured using a ⁷Li ion beam and a windowless gas target system filled with D₂ gas. The proton yield of the reaction and the β-delayed α-activity of the residual nuclides ⁸Li were observed both concurrently with the elastic scattering yield, relating σ to the Rutherford scattering cross section σ_R. The resulting values, σ (from p) = 143.6 ± 8.9 mb and σ (from ⁸Li) = 151 ± 20 mb, lead to a weighted mean value of σ = 153 ± 6 mb (χ² = 2.26) including all available values and σ = 146 ± 5 mb (χ² = 0.05) removing some values from the data set. The consequences for the expected flux of high-energy solar neutrinos are discussed.