X-ray spectroscopic study of chemical bonding in NiSe and NiSe2

The K absorption spectra of nickel and selenium have been recorded photographically in the pure metals and the compounds NiSe and NiSe₂. It has been observed that the Ni discontinuity shifts toward the high energy side with respect to that in the pure metal by about 5.0 eV for NiSe and about 6.7 eV for NiSe₂. The Se edge in both these compounds is found to shift by about 2.6 eV toward the low energy side with respect to that in pure selenium. From these results it is possible to obtain the bonding pictures for the compounds. The compound NiSe appears to have resonating p³ type of bonding. For NiSe₂ the orbitals involved in the bonding are d²sp³ for the metal atom and sp³ for the metalloid atom. The electrical behaviour of the compounds has been explained on the basis of these bonding pictures.     

Relative strengths of the competing multipoles in the K and L series x-ray spectra in theNR limit

For most of the transitions of theK andL series x-ray spectra the ratio of the contributions of the competing multipoles, δ², is independent of the radial matrix element in the non-relativistic limit. In the present paper calculations of δ² are made in the non-relativistic limit which give the relative strengths of the two closely competing electric and magnetic multipoles. The dominant mode in the emission processes of the transitions in theK andL series x-ray spectra has been assigned on the basis of these calculations.     

Spectroscopically determined electronegativity values for heavy elements

A new scale of electronegativity based on X-ray spectroscopic data was earlier presented by Mande and others for the elements₃Li to₅₄Xe. The present paper reports an extension of this scale carried out for most of the heavier elements lying between₅₅Cs and₉₂U. The present approach is based on the physical interpretation of electronegativity of an atom as the attractive electrostatic force it exerts at a distance equal to its covalent radius. To estimate this force, experimental spectroscopic data have been employed. The merits of such an approach have been pointed out recently by Mullay and may be of interest in the context of the intimate relation found between electronegativity and superconducting transition temperature.     

The shapes of the LIII X-ray absorption discontinuity of rhenium in compounds

The X-ray L_III absorption edge of rhenium in the pure metal and in two compounds, namely, K₂ReCl₆ and KReO₄ has been studied using a Cauchois type bent crystal spectrograph of 40 cm diameter. The splitting of the main absorption discontinuity has been observed for the first time in the compounds. This splitting and the edge structure of the Re L_III discontinuity in the compounds have been interpreted on the basis of molecular orbital diagrams. The crystal field splitting, Δ, has been determined experimentally in both the compounds in the solid state.     

X-ray spectroscopic study of chemical bonding in MnSe2 and CoSe2

X-ray absorption study of two intermetallic compounds MnSe₂ and CoSe₂ has been carried out using a Cauchois type bent crystal spectrograph. The metal K absorption edges in both the compounds are found to shift toward the high energy side with respect to the discontinuities in the pure metals. On the other hand, the Se K absorption edge in both these compounds is found to shift toward the lower energies. Emission study of the compound MnSe₂ has shown that the Mn Kβ ₅ band in this compound is shifted toward the high energy side with respect to that in the pure metal. From the magnetic data and the results obtained in this work it is possible to obtain the chemical bonding pictures in these compounds. For MnSe₂ the bondings sp ³ d ² for the metal atom andsp ³ for the metalloid atom have been suggested. For CoSe₂ the bondings appear to bed ² sp ³ for the metal atom andsp ³ for the metalloid atom. These bondings are compatible with the pyrite type structure of these compounds. It is possible to explain the electrical behaviour of the compounds on the basis of these bonding pictures.     

Plasmon excitation in the x ray absorption process

A simple approach is developed to study the excitation of a plasmon due to valence electronic correlations in the x ray absorption process. Assuming a complete separation between the core and the valence electrons, we introduce the plasmons in the system Hamiltonian externally according to the Bohm-Pines collective formalism and carry out the corresponding canonical transformations to separate the x ray photonplasmon-electron term. According to our calculations, the relative intensity of the plasmon process with respect to the main absorption, which represents single particle excitations is 0·12 times the interelectronic separation measured in Bohr radii. The theoretical estimates of the plasmon intensity agree satisfactorily with the experimental values for the Mn K and the Re L_III absorption discontinuities. The shape of the plasmon absorption band resembles the main absorption edge, if the wave vector dependence of the plasmon frequency is neglected. The intensity of the second plasmon harmonic is about 3 per cent of the first plasmon satellite spectrum. The electron plasmon interaction modifies the shape of the plasmon spectrum.     

Molecular orbital interpretation of the rhenium LIII absorption discontinuity in some compounds

The shapes and the fine structure of the X-ray L_III absorption discontinuity of rhenium have been studied in seven octahedral and three tetrahedral compounds using a Cauchois type 40 bent crystal spectograph. The main absorption discontinuity is found to be split into two compounds for all the compounds. This splitting and the near edge structure have been interpreted with the help of qualitative molecular diagrams.     

An NMR study of the thiomalic acid complex of cobalt

An NMR study of the thiomalic acid complex of cobalt has been carried out at pH 2.6. The results show that the freshly prepared complex is paramagnetic and it gradually changes to the diamagnetic state, the reaction being complete in about 24 hours. It has been shown that the fresh complex has the hybridization sp³d², whereas the stable complex has the hybridization d₂sp₃. The results have been confirmed by measuring the change in the magnetic susceptibility of the complex with time.     

X-ray spectroscopic study of the thiomalic acid complex of cobalt

The cobalt K absorption spectrum has been studied in thiomalic acid complex of cobalt using a bent crystal X-ray spectrograph. It has been observed that the position of the absorption discontinuity taken with the freshly prepared complex differs from that of the discontinuity obtained with the complex kept in air for about 24 hours. It has been shown that this shift of the absorption edge is due to the change in valency of cobalt in the complex. The shape of the absorption discontinuity has revealed that the complex has an octahedral structure with the hybridizationsp ³ d ². On the molecular orbital theory the electronic configuration in this complex can be described asa _1g ^Emphasis>2 t _1u ^Emphasis>6 e _g ^Emphasis>4 t _2g ^Emphasis>4 e _g ^Emphasis>*2 .     

Modification of Lytle’s theory: Interpretation of the extended fine structure associated with LIII absorption discontinuity of some ytterbium systems

In Lytle’s theory for the extended fine structure in x-ray absorption spectra, the potential at the boundary of the ‘equivalent sphere’ around the absorbing atom, having volume equal to that of the Wigner-Seitz cell is considered to be infinite. It has been observed that Lytle’s theory is applicable only in the case of metals and metallic systems. In the present paper the extended fine structure associated with the L_III absorption spectra of some systems of ytterbium is interpreted on the basis of Lytle’s model, modified by using a finite potential instead of an infinite one at the boundary of the equivalent sphere. The values of this potential are estimated for eight systems of ytterbium. It has been shown that there exists a correlation between the potentials and covalency of the compounds.