Differential elastic and quenching cross sections for Ar*(3P) and CO2(X1 ∑ g +)

The energy dependence of the differential scattering of metastable Ar*(³P) by ground-state CO₂(X¹ ∑ _g ⁺) has been studied at relative kinetic energies from 58 to 126 meV over an angular range of 5–160° c.m. using crossed molecular beams. The position and curvature of rainbow maxima, which are observed at each energy, are used to obtain parameters for a Lennard-Jones (12, 6) spherically symmetric potential. The position of the minimum, r _m = 5·02 ± 0·65 Å, is identical to that for K + CO₂ and the well depth, ε = 16·3 ± 0·8 meV, is about 10 per cent greater. The scattered intensity shows a distinct fall-off on the dark side of the rainbow compared to that expected for elastically scattered Ar*. This depletion, caused primarily by the quenching of Ar*, is analysed in terms of the optical-shadow model to determine the energy dependence of the observed quenching cross section, which is predicted to have a maximum of 67 Ų at 193 meV.     

Ab initio intermolecular potential energy surface of Ne···NCCN van der Waals complex: effect of the place of midbond function on the interaction

The intermolecular potential energy surface of Ne···NCCN van der Waals complex was evaluated in the framework of the counterpoise-corrected supermolecular approach using CCSD(T) level and aug-cc-pVDZ basis set extended with a set of midbond (3s3p2d1f1g) functions. The effect of the place of midbond function on the accuracy of the calculated potential energy surface was examined and the optimised position for placing midbond function was determined. The calculated potential energy surface was fitted by an analytical function. The analytical function of intermolecular potential energy surface of Ne···NCCN demonstrated a global minimum energy of ?12.024 meV related to the T-shape geometry at the distance between Ne and the centre of mass of NCCN of 3.28 Å. Finally, the interaction second virial coefficients (B₁₂) of Ne and NCCN were calculated and used to calculate the second virial coefficients for the mixture of neon and cyanogen gases at different mole fractions of Ne gas.     

Formulae which relate pressure,activity and potentials of mean force to sums of integrals over Ursell-Mayer correlation functions of the distribution functions

The pure rotational spectrum in the far-infrared between 30 and 170 cm^-1 and its absolute intensity has been measured for CH₂D₂ in the vibrational ground state by high-resolution interferometric Fourier transform techniques. The analysis of the integrated cross-sections in the essentially water-free spectrum results in an accurate value for the permanent, vibrationally induced ground state electric dipole moment of CH₂D₂|μ₀| = (6·40±0·33) x 10^-3D.The influence of centrifugal effects on intensities and on the determination of the permanent dipole moment was investigated. Although centrifugal effects are important for the explanation of single band profiles, they appear to be of little relevance for the resulting permanent dipole moment. A new, more general 9- dimensional dipole moment function for methane is derived from ab initio calculations and experimental band strength information of CHD₃. Quantum Monte Carlo calculations using this function and a new, more general 9- dimensional analytical, anharmonic potential function for methane yield a semi-theoretical estimate μ₀ ^z = – (7·8±0·5)x10^-3D for CH₂D₂.     

On the calculation of the orientational correlation parameter g 2

The g ₂ factor for a model of liquid carbon disulphide has been calculated by molecular dynamics simulation. The values of g ₂ for the model at three points along the orthobaric curve are: 1·17 ± 0·04 (298 K), 1·27 ± 0·03 (245 K), 1·39 ± 0·06 (193 K). These values are in good agreement with available experimental values. By calculating g ₂ in shells of cubic symmetry it is found that the value of g ₂ is determined by the orientational correlation of a molecule with neighbours within a few (two to three) molecular diameters. Spurious orientational correlations are introduced by the periodic boundary conditions and the calculation of collective correlation functions by averaging over the whole cube is shown to be unreliable. A theoretical calculation of g ₂ using RISM + SSA fails to reproduce the state dependence of the g ₂ values calculated from the simulation. This failure is not due to the small differences between the simulation and RISM g _αβ(r) for r < 4·5 Å but to inaccuracies in the SSA in the intermediate region r ～ 6 Å.     

Optical absorption and electrical conductivity of flash evaporated CuGaTe2 thin films

The optical absorption edge of CuGaTe₂ thin films in the energy range 1 to 2·3 eV was studied. The characteristic band gaps were found to be 1·23 eV and 1·28 eV whereas the acceptor ionization energy was 170 meV. Electrical conductivity measurements were carried out in the temperature range 300–550 K and two acceptor states with ionization energies 400 meV and 140 meV were found. The origin of acceptor states is explained based on covalent model.     

Spin waves in MnO; from 4°K to temperatures close to TN

Spin waves have been measured in MnO by inelastic scattering of neutrons from 4 °K to a temperature 0·25 °K below T_N. The 4 °K spectrum is interpreted in the frame of linear spin wave theory with effective exchange integrals J₁^? = 0·321 meV, J₁⁺ = 0·424 meV, J₂¹ = 0·446 meV and a phenomenological parameter for anisotropy D₁ = 0·059 meV. The effect of the actual dipole-dipole Hamiltonian is shown to give a priori a very good account of the lifting of the degeneracy of spin waves near the Brillouin zone center. The Bloch model for interacting spin waves and theories based on Green function approximations have been adapted to the MnO case, in order to compute the main properties (mean magnetization of a sublattice, anisotropic deformation, extra isotropic contraction and magnon spectrum) at many temperatures. Comparison of these with experimental results tends to favour a generalized Callen renormalization model, which gives an overall fit from 4 °K, to temperalures close to T_N.     

Specular reflection of helium and hydrogen molecular beams from the (111) plane of silver

The Debye—Waller (DW) factor in the specular reflection intensity of He and H₂ molecular beams from the Ag (111) plane has been studied experimentally and theoretically. A new expression for the DW factor corrected for a stationary part of the gas—surface interaction potential is derived kinematically and semi-classically by the use of a Morse potential. An analysis of the experimental data through the above DW factor yields a surface Debye temperature of 251 ± 20 K, which is unusually high, and potential depths of 1.5 ± 1.0 meV for He and 6.4 ± 2.9 meV for H₂, which seem slightly too small. These results are discussed on the basis of the nature of gas-surface interactions and in comparison with the results deduced from the conventional DW factor corrected for a constant attractive potential depth.     

MBPT studies of van der Waals molecules

The many-body perturbation theory is employed for the calculation of the interaction potential for the F^- … He system in the framework of the supermolecule method. A particular attention is paid to the choice of the basis set functions for the two subsystems and the related basis set superposition effects. It has been found that the main features of the interaction potential are recovered in the SCF approximation. The SCF potential has its minimum at the distance R = 6·4 a ₀ with the interaction energy of 53 cm^-1. The complete fourth-order MBPT method gives the potential minimum position and depth equal to 6·5 a ₀ and 64 cm^-1, respectively. The basis set superposition effects estimated by using the counterpoise technique are negligibly small for the SCF interaction potential, while at the correlated level their magnitude is comparable to the value of the total correlation contribution to the interaction energy. The basis set superposition effect in calculations of the electron correlation contribution to weak intermolecular interactions is found to be the major factor limiting the reliability of the corresponding theoretical data.     

Magnetically stabilized electron-hole liquid in indium antimonide

Luminescence spectra of sufficiently pure n-type indium antimonide crystals (N _D−N _A=(1–22)·10¹⁴ cm⁻³) in a magnetic field of up to 56 kOe, at temperatures of 1.8–2 K, and high optical pumping densities (more than 100 W/cm²) have been studied. More evidence of the existence of electron-hole liquid stabilized by magnetic field has been obtained, and its basic thermodynamic parameters as functions of magnetic field have been measured. When the magnetic field increases from 23 to 55.2 kOe, the liquid density increases from 3.2·10¹⁵ to 6.7·10¹⁵ cm⁻³, the binding energy per electron-hole pair rises from 3.0 to 5.2 meV, and the binding energy with respect to the ground exciton level (work function of an exciton in the liquid) rises from 0.43 to 1.2 meV. Zh. éksp. Teor. Fiz. 111, 737–758 (February 1997)     

Au(110)表面结构和氧原子吸附的第一性原理研究

用密度泛函理论(DFT)研究了金属Au(110)表面结构以及氧原子的吸附状态.计算得到Au(110)-(1×2)缺列再构表面原子的弛豫分别是-15.0%(Δd₁₂/d₀)和-1.1%(Δd₂₃/d₀),表面能为52.7 meV/²,功函数Φ=5.00 eV;Au(110)-(1×3)缺列再构表面的Δd_{1 关键词： 缺列再构Au(110)表面 STM图像 氧原子吸附}     

A computational study of N2···HHeF: comparison with N2···HArF and N2···HKrF

A weakly bound linear complex of N₂ and HHeF was found to be stable with respect to the constituent monomers by ab initio calculations at various levels of theory (MP2, MP3, MP4(SDQ) and QCISD) using a 6-311++G(2d,2p) basis set. The complex N₂···HHeF was found to have a zero-point vibrational energy corrected binding energy of 14.5?kJ mol^?1 (QCISD) and exhibits a large harmonic vibrational frequency blue shift of 375?cm^?1 for the He–H stretching vibration mode, with a diminished infrared intensity for this mode on formation of the complex. The frequency shift for this mode was also found to be very sensitive to the level of theory employed for the calculation, and is rationalized by considering intermolecular electrostatic and charge-transfer effects. The results for N₂···HHeF are compared with corresponding results for the related complexes N₂···HArF and N₂···HKrF, both of which contain the same proton acceptor molecule.     

Shallow donor in natural MoS2

Using electron paramagnetic resonance and density functional theory calculations, we show that the shallow donor responsible for the n‐type conductivity in natural MoS₂ is rhenium (Re) with a typical concentration in the low 10¹⁷ cm^–3 range and the g ‐values: g_|| = 2.0274 and g_⊥ = 2.2642. In bulk MoS₂, the valley–orbit (VO) splitting and ionization energy of the Re shallow donor are determined to be ～3 meV and ～27 meV, respectively. Calculations show that the VO splitting of Re approaches the value in bulk if the number of MoS₂ layers is larger than four and increases to 97.9 meV in a monolayer. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Analytical ab initio computation of force constants and dipole moment derivatives: LiH,Li2 and BH

Ab initio calculations of harmonic force constants and dipole moment derivatives have been performed for the diatomic molecules LiH, Li₂ and BH, using Hartree-Fock perturbation theory for a series of spherical gaussian SCF-MO wavefunctions. The results of these computations support the conclusion made in a previous paper that the so-called general method of calculation is the most reliable. The results obtained with the energetically best wavefunctions are (experimental values in parentheses, atomic units throughout): Force constants: LiH 0·071 (0·066); Li₂ 0·019 (0·016); BH 0·210 (0·196). Dipole moment derivatives: LiH - 0·48 (-0·42±0·06); BH - 0·67 (-0·4).     

Symmetry enforced gauge invariance of nuclear magnetic shielding constants

E.S.R. experiments performed at 1·3 K by optical detection are reported for the photo-excited triplet state of palladiumporphin in a single crystal of n-octane, and the observation of a level anticrossing signal is described.

In the crystal the orbital degeneracy of the ³ E _u state of the free molecule is lifted by the crystal field and in n-octane the energy difference between the two orbital components |x> and |y> is found to be 58 ± 2 cm^-1. The spinorbit coupling (SOC) and the orbital Zeeman interaction couple the triplet manifolds of |x> and |y>, and for a proper understanding of the magnetic properties of these states it is necessary to work in the basis of the six spin-orbit functions deriving from the ³ E _u state of the free molecule. It is shown that either of the two triplet states can be described by an effective spin hamiltonian of the common form and expressions for the zero-field parameters D and E and the principal values of the g tensor are given. The experimental values of the parameters in the lowest triplet state are D = -24·38 ± 0·03 GHz, |E| = 320 ± 60 MHz, g _‖ = 1·677 ± 0·001 and g _⊥ = 1·989 ± 0·002. The matrix element of the SOC connecting the |x> and |y> triplet manifolds amounts to qZ = 15 ± 3 cm^-1 and the vibronic orbital angular momentum (in units of ?) in the ³ E _u state of the free molecule to qΛ = 1·5 ± 0·3. A tentative value of 0·63 for the orbital reduction factor q is obtained by comparison with a theoretical estimate of Λ. The value of q is indicative of weak Jahn-Teller coupling.     

Proton N.M.R. study of the dynamics of the ammonium ion in ferroelectric langbeinite, (NH4)2Cd2(SO4)3

The proton N.M.R. lineshape of polycrystalline Langbeinite, (NH₄)₂Cd₂(SO₄)₃, has been studied in the temperature range 300 K to 1·8 K. The resonance line is motionally narrowed over the entire temperature range, and the low temperature proton line shows clear evidence for tunnelling motion of the ammonium ion between spin-symmetry states. From a computer simulation of the lineshape, we obtain an estimate for the tunnelling splitting parameter, J, of the torsional ground state of the ammonium ion, as 375 ± 125 gauss. For an undistorted tetrahedral crystal field this corresponds to a tunnelling splitting Δ = 4J = 6·3 ± 2·1 MHz.

Pulsed proton N.M.R. studies have also been carried out on the above compound at 30·8 MHz and 48·2 MHz and the spin-lattice relaxation time (T ₁) has been measured by the π - t - π/2 pulse sequence as a function of temperature down to 77 K. At 30·8 MHz, a T ₁ minimum of 13 ms occurs at 105·8 K, and is ascribed to random reorientations of the NH₄ ⁺ ion. An activational energy barrier of 0·74 ± 0·1 kcal/mole and an associated pre-exponential factor of 8·0 × 10^-13 s are calculated for the above motional process, and the value of the activation energy is correlated with the tunnelling splitting of the torsional ground state.

An anomaly in T ₁ has been observed at the ferroelectric Curie point (95 K), indicating the order-disorder nature of the transition. This is the first experimental evidence relating to the nature of the transition in Langbeinite.     

Zeeman spectroscopy of the 4 Eu → 2 B 1g phosphorescence of copper porphin in an n-alkane single crystal

The phosphorescence spectrum of the metastable ⁴ E_u state of copper porphin in single crystals of n-octane (C₈) and n-decane (C₁₀) has been studied between 2·3 and 35 K, with and without a magnetic field B. The crystal field splitting between the orbital components observed at 35 K is δ = 30·3 ± 0·3 (C₈), 13·8 ± 0·2 cm^-1 (C₁₀). From the Zeeman shifts we derive the effective orbital angular momentum Λ′ = 0·8 ± 0·2 (C₁₀), the spin-orbit coupling parameter |Z′| = 1·5 ± 1·0 cm^-1 (C₁₀), the spin-spin dipolar interaction parameters D = -0·1 ± 0·2 cm^-1 (C₈, C₁₀) and |E| = 0·31 ± 0·03 cm^-1 (C₈, C₁₀), and the g-factors g _∥ = 2·14 ± 0·04 (C₈, C₁₀) and g _⊥ = 2·00 ± 0·03 (C₈, C₁₀).     

Determining potential energy constants for atom- and molecule-surface interactions

Methods developed for diatomic molecule spectroscopy are adapted for use in analysing the energies of atom-surface bound states in order to determine certain features of the surface-averaged potential energy function. In cases for which appropriate data are available, these simple graphical methods can yield a model-independent estimate of the potential well depth e, a value for the coefficient (C₃) of the long-range z^?3 term in the atom-surface potential, and estimates of both the total number of bound states and the energies of any unobserved levels lying near the dissociation limit. Application of these techniques to the data for atomic hydrogen on (001)LiF and NaF and for atomic helium on (001)LiF yielded: ? = 18.6(±1.0), 18.2 (±3.6) and 8.6(±0.8) meV, and C₃ = 250(±90), 180(±110) and 95(±40) meV ų, respectively. Application of this approach to the data for molecular hydrogen on (001)LiF led to a new set of vibrational assignments and showed that ? = 37(±4) meV, and that the H₂ and D₂ data of O'Keefe et al. and the H₂ binding energies which Tsuchida obtained from the data of Frisch and Stern are all internally consistent.     

Optical and electrical properties of quantum wells with electrically tunable two-dimensional electron density by selective contacts

We report on photoluminescence and absorption measurements in type-I hetero n-i-p-i structures. The electron density in the pseudomorphic InGaAs/GaAs quantum wells is tunable between zero and more then 5 · 10¹² cm^-2. This electrical tuning of the subband filling is achieved by a variable voltage applied between selective n-and p-contacts fabricated by epitaxial shadow mask MBE. One of the advantages of having selective contacts to the n- and p-layers is to get reliable information about the electron density, independent of measured absorption and luminescence spectra. This allows a more rigorous analysis of the data on bandgap renormalization, bandfilling and k_∥-conservation. Moreover, the experiments can be performed at low optical power and low carrier temperatures. In the present investigation a bandgap renormalization of -20 meV and a bandfilling induced shift of the absorption edge as large as +50 meV was observed for a sheet electron density of 5 · 10₁₂ cm_-2.     

Analysis of hydrogen bonding and weak interactions in the crystal structure of (E)-N-(4-ethylphenyl)-2-(4-hydroxybenzylidene)thiosemicarbazone: experimental and theoretical studies

Hydrogen-bonding interactions play an important role in the rational design of crystal systems with desirable architectures. The novel thiosemicarbazone derivative described herein, namely (E)-N-(4-ethylphenyl)-2-(4-hydroxybenzylidene)thiosemicarbazone, C₁₆H₁₇N₃OS, (I), was prepared and characterised by ¹H NMR, IR and single-crystal X-ray crystallography techniques. The compound is arranged in the lattice by O–H···S and N–H···S bonded polymeric ribbons that extend along the crystal b-axis, and the intermolecular N–H···S hydrogen bonds formed R2 2(8) ring motifs. More importantly, C–H···π interaction stabilises the supramolecular structure of (I). Hirshfeld surface and their associated two-dimensional fingerprint plot analyses are presented to illustrate the supramolecular connectivity in the solid state. The result shows that the short H···H contacts is dominated in the total Hirshfeld surface. As well as we report on n→π* interactions in thiosemicarbazone derivatives by using the reduced density gradient function and natural bond orbital analyses. Besides, molecular electrostatic potential (MEP) and frontier molecular orbital (FMO) analysis of the title compound are also investigated by theoretical calculations.