Use of simulated infrared spectra to test N2-Ar pair potentials and dipole moment surfaces

Infrared spectra of the ¹⁴N₂-Ar van der Waals complex have been simulated by performing exact quantum mechanical calculations using two recent potential energy surfaces, one having a modified Morse-Morse-spline-van der Waals form and the other an exchange-Coulomb (XC) modelform. Frequencies and intensities have been calculated for some 10⁵ spectral transitions amongst the bound states of the complex, and simulations of the mid-infrared (2290-2370 cm^-1) spectrum of the complex at 77 K constructed from superpositions of lines, each of which has been assigned a Lorentzian lineshape with a linewidth appropriate to the experimental conditions. The roles of the various terms in the effective dipole moment surface proposed by Ayllon et al. (1990, Molecular Physics, 71, 1043) have also been examined, and a modification made which yields improved agreement with the experimental mid-infrared spectrum obtained by McKellar (1988, Journal of Chemical Physics, 88, 4190). Based upon the present calculations, the 48 most intense bands of the simulated spectrum of the ¹⁴N₂-Ar van der Waals complex have been given vibrational assignments. The spectrum simulated from the modified Morse-type potential surface, when employed together with the present modified dipole moment surface, shows distinctly better agreement with experiment than does the spectrum simulated from either the XC or the earlier empirical potential energy surface. Far-infrared spectra have also been simulated at 5 K and at 77 K using an appropriate effective dipole surface, and compared with the calculation of Ayllon et al.     

Theory of chemical bonds in metalloenzymes XX: magneto-structural correlations in the CaMn4O5 cluster in oxygen-evolving complex of photosystem II

ABSTRACT

Magneto-structural correlations in oxygen-evolving complex (OEC) of photosystem II (PSII) have been elucidated on the basis of theoretical and computational results in combination with available electron paramagnetic resonance (EPR) experimental results, and extended x-ray absorption fine structure (EXAFS) and x-ray diffraction (XRD) results. To this end, the computational methods based on broken-symmetry (BS) UB3LYP solutions have been developed to elucidate magnetic interactions in the active manganese catalyst for water oxidation by sunlight. The effective exchange interactions J for the CaMn(III)Mn(IV)₃O₅(H₂O)₃Y(Y = H₂O or OH^?) cluster (1) model of OEC of PSII have been calculated by the generalised approximate spin projection (GAP) method that eliminates the spin contamination errors of the BS UB3LYP solution. Full geometry optimisations followed by the zero-point energy (ZPE) correction have been performed for all the spin configurations of 1 to improve the J values that are compared with accumulated EPR in the S₂ state of Kok cycle and magnetic susceptibility results of Christou model complex Ca₂Mn(IV)₃O₄ (2). Using the calculated J values, exact diagonalisation of the spin Hamiltonian matrix has been carried out to obtain excitation energies and spin densities of the ground and lower excited states of 1. The calculated excitation energies are consistent with the available experimental results. The calculated spin densities (projection factors) are also compatible with those of the EPR results. The calculated spin densities have been used to calculate the isotropic hyperfine (A_iso) constants of ⁵⁵Mn ions revealed by the EPR experiments. Implications of the computational results are discussed in relation to the structural symmetry breaking (SSB) in the S₁, S₂ and S₃ states, spin crossover phenomenon induced by the near-infrared excitation and the right- and left-handed scenarios for the O–O bond formation for water oxidation.     

Computation and analysis of the dynamic structure factor S(k, ω) for small wave vectors

Molecular dynamics (MD) calculations have been performed for the Lennard-Jones (12-6) potential function using 2048 particles. Using conventional parameters the results may be compared with those for liquid argon.

The dynamic structure factor S(k, ω) has been determined both by Fourier inversion of the intermediate scattering function F(k, t) and from the longitudinal current-current correlation function C _∥(k, t). Particular attention was paid to the recurrence time of the system. The results for S(k, ω) by the two methods agree within 5 per cent for the whole region of small k-vectors considered. Double Fourier inversion of the van Hove function G(r, t) led to insufficiently accurate results for these small k-values. In view of the present data, the MD-results of Levesque et al. [1] for S(k, ω) have only a qualitative character. These latter data appear to contain truncation errors due to incomplete Fourier transformations.

Using a hydrodynamic assumption for F(k, t) we were able to extract the transport coefficients, the velocity of sound and the ratio of the specific heats in the limit of large wave lengths or small k. The velocity of sound was obtained by exploiting the MD generated anomalous dispersion curve of sound waves. Anomalous dispersion was found to set in for kσ ～ 0·25. A sound speed of 880 ms^-1 has been determined which is in excellent agreement with experimental values for liquid argon. The total error for the MD value amounts to about 5 per cent. In contrast, the ratio of the specific heats γ and the transport coefficients D _T and Γ (thermal diffusivity and sound attenuation) were determinable only with an accuracy of 15 per cent due to the need for larger extrapolations. Nevertheless, we found D _T, Γ and γ in agreement with experimental values within 5-10 per cent.     

Anisotropic angular distribution of sputtered atoms

The sputtering yield angular distributions have been calculated on the basis of the ion energy dependence of total sputtering yields for Ni and Mo targets bombarded by low-energy Hg⁺ ions. The calculated curves show excellent agreement with the corresponding Wehner's experimental results of sputtering yield angular distributions. This fact clearly demonstrates the intrinsic relation between the ion energy dependence of total sputtering yields and the sputtering yield angular distribution. This intrinsic relation had been ignored in Yamamura's papers [Yamamura, Y. (1982). Theory of sputtering and comparison to experimental data, Nucl. Instr. and Meth., 194, 515–522; Yamamura, Y. (1981). Contribution of anisotropic velocity distribution of recoil atoms to sputtering yields and angular distributions of sputtered atoms, Rad. Eff., 55, 49–55.] due to some obvious mistakes.     

Vibrational analysis of nitrosamine,a molecule with an almost constant potential along the inversion coordinate

ABSTRACT

The fundamental vibrational transitions of nitrosamine and its doubly deuterated isotopologue have been computed by vibrational configuration interaction theory including up to 6-tuple excitations. The potential energy surface has been represented by an n-mode expansion up to 4-mode couplings terms obtained from explicitly correlated coupled-cluster theory, CCSD(T)-F12a. Very good agreement with experimental data has been been achieved and a number of new assignments is provided.     

A quasiharmonic model calculation for non-markovian far-infrared spectra of HCl in Kr and Xe liquids

The far-infrared spectra (0–200 cm^?1) of dilute solutions of HCl in liquid Kr and Xe have been calculated by applying of a non-markovian spectral theory called PTOC (partial time ordering cumulants) and by using a quasiharmonic model for the liquid structure recently reported by us (A. Calvo Hernández et al., 1987, J. chem. Phys., 86, 4597) and successfully applied to HCl?Ar solution (Ibid., 86, 4607). The bath correlation functions which appear in the spectral theory involve a reduced set of parameters regarding both the HCl?Kr and HCl?Xe interactions and the liquid structure. From comparison between theoretical and experimental spectra it is possible to deduce quantitative values for the above parameters. The pronounced rotational fine structure of the experimental spectra for HCl in Kr and Xe liquids is quite well explained by the actual model.     

The F band of mixed ionic crystals as a function of temperature

Abstract

Experimental and theoretical study of the F absorption band were carried out in mixed ionic crystals as a function of temperature and molar composition. Both the point-ion and pseudopotential methods of Gourary–Adrian and Bartram–Stoneham–Gash, respectively, have been used to obtain the F band shift effect in KCl_1?x Br _x mixed crystals with molar fraction x and the temperature T of the crystal. The theoretical values were compared with the experimental ones, and a good agreement between experimental and theoretical calculations has been found.     

Stopping powers of Al,Ti, Cu,Zr, Rh,Ag, Ta and Au for 26 MeV alpha particles and Z3 1 correction

Abstract

Stopping powers of Al, Ti, Cu, Zr, Rh, Ag, Ta and Au for 26 MeV alpha particles have been measured using a surface barrier silicon detector with an accuracy of 0.35%. The stopping powers for alpha particles divided by 4 have been compared with the stopping powers for 6.500 MeV protons of the same velocity. Experimental magnitudes of the Z ³ ₁ correction which is contained in the Bethe-Bloch stopping formula were extracted using the alpha-proton difference. Using the experimental Z ³ ₁ corrections thus obtained and the experimental Z ³ ₁ corrections of the previous paper, parameters of γ and b which appear in the theory of Ashley, Ritchie and Brandt for the Z ³ ₁ correction have been determined with exactly the same method as the previous paper as γ = 1.336 and b = 1.32. The magnitude of the Z ³ ₁ correction calculated by the theory of Ashley, Ritchie and Brandt using these parameters have been compared with those obtained by other authors.     

Transport and relaxation properties of isotopomeric hydrogen–helium binary mixtures. I. H2–He mixtures

An extensive comparison has been carried out between calculated and measured bulk properties of H₂–helium mixtures. Detailed comparisons are presented for the interaction second virial coefficient, binary diffusion, mixture shear viscosity and thermal conductivity, rotational relaxation, thermal diffusion field-effects, collision broadening of the depolarized Rayleigh light scattering spectrum, and flow birefringence. Scattering calculations have been carried out for the ab initio potential energy surfaces obtained by Tao (1994, J. chem. Phys., 100, 4947) and Schaefer and Köhler (1985, Physica A, 129, 469). The values for the various bulk gas properties calculated from these two potential surfaces are generally found to lie within or near the experimental uncertainties.     

Influence of Coster-Kronig transitions on the polarization of L-shell x rays induced by proton impact

The alignment parameters for L ₃-subshells of Cd and Sb atoms are obtained by measuring the degree of polarization of the L ₁-lines excited by proton impact in the range from 0.1 to 0.5 MeV. To compare the experimental alignment parameter with theory, either experimental or numerical results must be corrected for Coster-Kronig (CK) transitions. The uncertainty in CK transition yields makes this comparison difficult. In this work, semiempirical values of the corrections have been derived from measured L-line intensities. The semiempirical correction factors exceed the theoretical ones. For constant reduced velocity, the semiempirical correction factor depends on the atomic number of the target. The semiempirical correction factor obtained in the same experiment improves the agreement between the theoretical alignment parameter and the experimental data. Zh. éksp. Teor. Fiz. 113, 2005–2010 (June 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

High pressure studies of sodium and silver halides

Abstract

We have investigated the structural phase transitions in sodium and silver halides theoretically under high compressions by means of first-principles self-consistent total-energy calculations within the local-density approximation using the full-potential linear-muffin-tin-orbital (FPLMTO) method. Our results confirm the recent high pressure experimental observations of crystallographic phase transformations in sodium halides (Leger et al. (1998) J. Phys.: Condens. Matter, 10, 4201) and silver halides (Hull and Keen (1999) Phys. Rev., B59, 750. The calculated transition pressures agree with the experimental data.     

Copper indium diselenide: crystallography and radiation-induced dislocation loops

Copper indium diselenide (CIS) is a prime candidate as the absorber layer in solar cells for use in extraterrestrial environments due to its good photovoltaic efficiency and ability to resist radiation damage. While CIS-based devices have been tested extensively in the laboratory using electron and proton irradiation, there is still little understanding of the underlying mechanisms which give rise to its radiation hardness. To gain better insight into the response of CIS to displacing radiation, transmission electron microscope samples have been irradiated in situ with 400?keV Xe ions at the Intermediate Voltage Electron Microscope facility at Argonne National Laboratory, USA. At room temperature, dislocation loops were observed to form and grow with increasing fluence. These loops have been investigated using g ?·? b techniques and inside/outside contrast analysis. They have been found to reside on {112} planes and to be interstitial in nature. The Burgers vector were calculated as b ?=?1/6 ?221?. The compositional content of these interstitial loops was found to be indistinguishable from the surrounding matrix within the sensitivity of the techniques used. To facilitate this work, experimental electron-diffraction zone-axis pattern maps were produced and these are also presented, along with analysis of the [100] zone-axis pattern.     

Pressure dependence of crystal structure and molecular packing in anthracene

Anthracene molecular crystal has been investigated up to a pressure of 10.5 GPa at room temperature using variable shape variable size Monte Carlo simulations in an isothermal–isobaric ensemble. We have reported various structural quantities, such as cell parameters and unit cell volume, as a function of pressure and compared them with the experimental results [J. Chem. Phys. 119, 1078 (2003)]. The pressure dependence of angles θ, δ and χ which describe the relative packing of molecules in the crystal has been calculated. We report that anthracene molecular crystal does not exhibit any first order phase transition up to a pressure of 10.5 GPa which is consistent with the experimental observations by Oehzelt et al. [Phys. Rev. B 66, 174104 (2002)]. The calculated equation of state (EOS) has been fitted to a Murnaghan-type EOS with good agreement. The calculated bulk modulus and the pressure derivative of bulk modulus are 8.2 GPa and 8.9 respectively which are in agreement with the experimentally calculated values.     

Momentum distribution and one-body density matrix in liquid3He.

Summary The momentum distributionn(k) and the one-body density matrix ρ₁(r,r' have been calculated in normal liquid³He atT=0. A variational wave function containing two-, three-body and backflow correlations has been used. The Fermi hypernetted chain technique has been employed and the elementary diagrams have been evaluated by the scaling approximation. The present estimate ofn(k) is in good agreement with the Monte Carlo data obtained with similar wave functions.n(k) and the discontinuityZ ofn(k) at the Fermi surface have been computed at several values of the density. The density dependence of the effective massm ^* has been found to be mainly due to that ofZ.     

Structural features of solid gallium in microporous glass

An experimental Debye-Scherrer study of structural features of gallium in porous glass with pore diameter d=4 nm is reported. Gallium structures different from the known bulk modifications have been discovered. Fiz. Tverd. Tela (St. Petersburg) 40, 1552–1553 (August 1998)     

A Numerical Calculation for Electron Impact Excitation of Copper

The scattering of electrons by atomic copper has been studied using Born approximation and the concept of the generalized oscillator strength (GOS). Differential and total cross-sections for the excitation of the 3d¹⁰ 4p² P state are calculated at incident energies of 100 eV and are compared with other available experimental and theoretical data. The agreement between our calculation for the differential cross-section and the available experimental results is fairly good at the forward angles, while the agreement at large angles is poor. The calculated total cross-sections are compared with the experimental data and those predicted by several theories. It is found that our calculation for the total cross-sections are in a good agreement with the close coupling calculation of Msezane and Henry (1986a, Physical Review A 33, 1631) for incident energies greater than 20 eV. The integrated cross-section measurements of Ismail and Teubner (1995, Journal of Physics B: Atomic, Molecular and Optical Physics 28, 4164) are in good agreement with the present calculation.     

Substituent effect on the electrochemical behaviour of some ortho-substituted (aryl)(2-nitrobenzo[ b ]thiophen-3-yl)amines. A combined experimental and computational study

The reduction potential values of the title compounds (1Ar,o) have been evaluated by cyclic voltammetry at a platinum electrode in the presence of 0.1?M N(Et)₄BF₄ in DMSO. Compounds 1Ar,o give reversible reduction peaks. The ortho-substituent affects their values basically by electronic effects (good LFER have been observed). The peculiar behaviour of (2′-hydroxyphenyl)(2-nitrobenzo[b]thiophen-3-yl)amine 1Ar,o(i) (showing two quasi reversible systems of peaks) has been explained on the basis of the special effect of the 2′-hydroxy substituent, which is able to assist a proton transfer through a network of hydrogen bonds involving the amine nitrogen atom (proton shuttle). This behaviour is unexpected in anhydrous DMSO and has similarities with the reaction features observed in water. The above hypothesis has been confirmed by quantum-mechanical DFT calculations carried out on 1Ar,o(i). In this theoretical investigation all the possible species, that can form as a consequence of two mono-electron reduction processes and the relevant various chemical transformations involving the intermediate species, have been carefully investigated.     

Specific heat of KTiOPO4 within the 80–300 K range

The specific heat of the KTiOPO₄ crystal has been measured with a vacuum adiabatic calorimeter within the 80–300 K range. A peak-shaped anomaly in the specific heat indicating a phase transition has been revealed in the C _p (T) curve at T≅279 K. Numerical integration of smoothened experimental C _p (T) curves yielded the thermodynamic functions of KTiOPO₄, namely, the entropy, enthalpy, and reduced Gibbs energy. The entropy and enthalpy of the observed transition have been determined. Fiz. Tverd. Tela (St. Petersburg) 41, 497–498 (March 1999)     

Intrinsic <Emphasis Type="Italic">g</Emphasis><Subscript><Emphasis Type="Italic">K</Emphasis></Subscript> factors of odd-mass <Superscript>167–179</Superscript>Lu isotopes

In this paper, g _K -factors of the intrinsic magnetic moments and effective spin gyromagnetic factors (g _s^eff) of the ^167–179Lu isotopes have been studied within the Tamm-Dancoff approximation (TDA) (Kuliev et al, Sov. J. Nucl. Phys. 9, 185 (1969)) by using a realistic potential such as Woods-Saxon potential for the first time. The effects of the spin-spin and spin-isospin interactions on magnetic moments were investigated. The results of the theoretical calculations are compared with the experimental data for related nuclei. The experimental values of g _K and g _s^eff were computed from the observed magnetic moments (Georg et al, Eur. Phys. J. A3, 225 (1998)) using the spin matrix elements. The theoretical predictions for the g _K factors exhibit good agreement with the experimental g _K factors with increasing mass number A of the lutetium isotopes. The strongest influence of the neutron-proton spin interaction occurs at q = −1. Sufficient agreement between the calculated and the experimental values of g _K is obtained for κ = (45/A) MeV and q = −1.