An ESCA investigation of some copper complexes

A series of copper complexes have been investigated by ESCA. All complexes were salts of the tetraphenylphosphonium ion. The binding energies of all the atoms in the complexes were determined. From the binding energies of the ligand atoms we estimated the effective charges on these atoms. For this purpose we used linear relations of the formE_b = kq + E_bO which had been established previously within our scheme of C 1s (phenyl) as internal standard. From the data thus obtained, the effective charge on the copper atom was estimated. A linear relation between binding energy and the effective charge on the copper atom was found, i.e.,E_b(Cu) = 1.52q_Cu + 932.2ESCA spectra were recorded for the complexes bis(1,3-diphenyl-1,3-propanediono) copper (II) and bis(3-phenyl-2,4-pentanediono) copper (II). By a combination of the XPS binding energies and IR intensities of the ν_CH vibrations of the phenyl groups in the complexes with empirical relations between these entities and the effective charges of the atoms and groups, a fairly complete mapping of the charge distributions of these complexes has been achieved.     

An ESCA investigation of some thiocyanato complexes

A series of simple thiocyanato complex ions have been investigated as their tetraphenylphosphonium and potassium salts. The binding energies of N, C and S were determined as well as those of the metals. From the first-mentioned data effective charge-values were estimated for the atoms of the ligands. For this purpose linear relations E_b = kq + E_b0 were used that had been previously established within a scheme having C_1s (phenyl) as the internal standard.From the data thus obtained the effective charge on the metal atoms was estimated. For elements where we have sufficient data the same type of linear relation seems to he followed. Tentatively valid examples are E_b(Ni) = 6.74q_Ni + 848.3 eV and E_b(Pd) = 4.45q_Pd + 333.9 eV.In this interpretation the atoms of the metals are considered to be positively charged and surrounded by the negative charge of the electrons occupying the s band.It is further suggested for complexes with pronounced π backbonding (Pt(SCN)₄^2?, Pd(SCN)₄^2? and Hg(SCN)₄^2?) that the C 1s binding energy measured for the carbon atom of the SCN^? ligand is composed of the ionisation energy from the 1s level and an additional term corresponding to the intraligand π → π* transition.     

On the core electron binding energy of carbon and the effective charge of the carbon atom

From Mulliken population data based on ab initio calculations of a series of substituted aromatic compounds and from well-calibrated XPS data (core electron binding energies, E_b) an empirical relation between E_b(C1s) and the charge on the carbon atoms, q_c, has been found: E_b(C1s = 6.42q_c + 4.52q²_c + 285.8 (eV). It is also found that XPS data for other carbon-containing species, notably the cyanide ion, can be described by this relation.     

Effective charges in sulfur nitrides from ESCA spectra: A test of the method of internal calibration

A method for internal calibration of solid-state ESCA spectra is described that permits the use of the simple relation between binding energy E_b and charge q:E_b = kq + E_b0 for a surprisingly large number of elements. In order to test these relations for S and N, a procedure is suggested that allows the calculation of the effective charges on S and N in S₄N₄, S₂ N₂ and (SN)_x from gas-phase or uncalibrated ESCA data. The agreement with theoretically calculated values is good.     

ESCA Studies on Silicon Compounds Using an Internal Standard for Calibration

X-ray photoelectron spectra (ESCA) for some silicon compounds have been measured. As an internal standard the Cls binding energy of the carbon atoms of incorporated phenyl groups have been used. The actual value of this binding energy was determined from a previously found relation between E_b Cls and the infrared absorption intensity (A_CH) of the C-H stretching vibrations of the phenyl group.

In this way a correlation between the binding energy of the silicon atom (Si2p) and its effective charge (q_Si) could be set up: E_b = 1.53 q + 100.6. The charges were quoted from quantum chemical calculations in literature or derived from a previously reported relation between the infrared absorption intensity (A_CH) and total charge of the phenyl group in compounds of the type C₆H₅X.     

Lattice vibrations of AsxP1−xIn solid solutions

On the basis of investigations of reflection spectra from As_xP_1?xIn solid solutions, new data have been obtained on the character of the vibrational spectrum for compositions in which x is, 0, 0·2, 0·3, 0·4, 0·5, 0·6, 0·8, 0·9 and 1. The variation of the frequencies and oscillator strengths that characterize As and P atom vibrations has been determined as a function of composition. From the comparison of calculated with experimental reflection spectra, the dispersion of the real part (∈₁) and the imaginary part (∈₂) of the dielectric constants of the substance as well as |∈| have been estimated. The values of the nonlocal and local parts of the effective ion charge of InAs and InP were also determined.     

Effect of the target density on the cross section of charge exchange between fast ions and atoms

When fast X^q+ X^{q^ + } ions collide with atomic or molecular targets, the total charge exchange cross section decreases with increasing target density. This is because the excitation levels of resulting X^{(q - 1)+} X^{(q - 1)^ + } ions are suppressed because of ionization by target atoms. The effect of target density on the total charge exchange cross section may amount to one order of magnitude or more depending on the charge and energy of an incident ion, as well as on the density and inner shell configuration of target atoms. Numerical calculations are performed for partial (in the principal quantum number n) cross sections σ(n) and total cross sections σ_tot=Σ_nσ(n) of charge exchange in the case of collisions of fast multiply charged ions having an energy E in the range 100 keV/u-10 MeV/u with gas or solid targets.     

Relationship between cation–π and anion–π interactions: individual binding energies in the π–Mz+–π–X−–π system

The mutual influence of cation–π and anion–π interactions in the π–M^z+–π–X^?–π system (M^z+ = Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, Ca²⁺ and X^? = F^?, Cl^?) has been studied by quantum mechanical calculations. Both geometric parameters and energy data reveal that cation–π and anion–π interactions enhance each other in the π–M^z+–π–X^?–π system. Individual binding energies (E_ion···π) have been estimated in the quintuplet system using a simple new method from electron charge densities calculated at the bond critical points (BCPs) of the ion···π interaction by the atoms in molecules (AIM) method at the M062X/6-31+G(d) level of theory. With respect to the obtained individual binding energies, the strength of an ion···π interaction depends on the cooperative effects of other components.     

Chemical shifts of the LIII absorption discontinuity of rhenium

Chemical shifts of the X-ray L_III absorption discontinuities of rhenium in some of its binary and ternary compounds have been studied using a bent crystal X-ray spectrograph. The chemical shifts (ΔE) are found to be governed by the effective charges (q) on the absorbing ions, which have been calculated using Suchet's theory. For the compound ReCl₅, however, the effective ionic charge cannot be calculated since the pentavalent radius of rhenium is not known. The ΔE, q plot has been used to determine the charges on the rhenium ions in ReCl₅ as well as in two ternary compounds KReO₄ and NaReO₄. Our work has enabled us to determine the ionic radius of pentavalent rhenium.     

An analytic calculation of the weak field limit of the static color dielectric constant

We analyze the Dyson equation/Ward identity system for the axial gauge n · A = 0 gluon propagator Δ_μν(q)whenn · q = 0. The solution behaves like (q^?4 + (q²)^ν?1) for small q₂, and we are able to calculate the power ν analytically. It turns out to be 0.1737. This analytic calculation verifies our earlier numerical solutions to these equations. For static problems, n · q = 0 is the temporal gauge, and in this gauge the gluon propagator is directly related to the color dielectric constant. We can thus calculate the dielectric constant in the infrared limit.     

Winkelverteilung der Kernphotoreaktion3He (γ,p)2H

The angular distribution of the photonuclear reaction³He(γ,p)²H was measured with an exitation energyE _x=16 to 27 MeV using a 32.5 MeV betatron. In agreement with a theoretical calculation of Böschet al. we found for the coefficients of the distributionf(θ)=b (a/b+sin²θ(1+β·cosθ+γ·cos²θ)) the values:a/b≦0.14; β=0.77 (+0.14; ?0.07); γ≦0.30. This was the first attempt to use spark chambers as a detection device for photonuclear reactions in the low energy range. We found it to be a promising new facility.     

Theoretical investigation of the backbone···π and π···π stacking interactions in substituted-benzene||3-methyl-2′-deoxyadenosine: a perspective to the DNA repair

The π-stacking effects of substituted benzenes on the N-glycosidic bond strength of 3-methyl-2'-deoxyadenosine (3-MDA) were studied by quantum mechanical calculations. Although all substituents enhance the stacking interactions, enhancement is higher for the electron-donating (ED) substituents. When the overall binding energy is separated into the π···π (ΔE_π···π) and backbone···π (ΔE_bb···π) contributions, the ED and electron-withdrawing (EW) substituents increase those contributions, respectively. Both the ED and EW substituents decrease the distance between the centres of stacked rings, while the EW ones increase the N-glycosidic bond length. The electron charge density calculated at the C--N bond critical point (ρ_C–N) is in linear correlation with the backbone···π interaction, not with the π···π interaction. This study also shows that the charge transfer from X-Ben to 3-MDA is in linear correlation with the ΔE_π···π and the change in the charge on the sugar ring is in better accordance with the backbone···π interaction. The N7 proton affinity (PA_N7), with a key role in the depurination process, is highly affected by the π···π interactions. Thus, both interactions must be considered because of the balance between the backbone···π and π···π contributions in these biomolecular systems.     

Studies on the opto-electronic properties of III–V and II–VI group semiconductors from optical electronegativities

New empirical relations have been proposed to evaluate bond energies (E_s) in compound semiconductors, first from the knowledge of optical electronegativities of the constituent ions and secondly from the energy gap values. The validity of the two relations has been tested in the case of certain III–V and II–VI group semiconductors by comparing the calculated values of E_s, with those in the literature. From the computed values of E_s, refractive indices have been calculated. The Penn gap (E_p), Fermi energy (E_F) and S_o-parameter for these semiconductors have also been determined. The estimated values of these parameters are utilized to evaluate the electronic polarizabilities (α). The computed values of a compare excellently with the standard data.     

Effective charge in the II–VI and III–V compounds with zincblende or wurtzite type structure

The effective charge in the II–VI and III–V compounds was analyzed by using a linear chain model. On the assumption that the ionic lattice is immersed in a cloud of valence electrons with the dielectric constant of ?(∞) = n²?₀ (n: refractive index, ?₀ = 8·85 × 10^?12f/m), the effective charge on an ion is equal to 2e in the II–VI compounds and to e in the III–V compounds (e: electronic charge), respectively. These values of the effective charge are just n times the Szigeti charge.Although direct connection between neighboring atoms is the main part of the binding force, the fact can not be neglected that the second nearest neighbor atoms are connected by sharing some of valence electrons between them. The electrons in valence bonds contribute to the refractive index and are estimated to be e and 2e per atom in the II–VI and III–V compounds, respectively.     

Final state effect for Au 4f line from gold-nano-particles grown on oxides and HOPG supports

The effect of a positive charge left to a small metal particle immediately after photoemission, so called the final state effect is studied for Au 4f binding energy (E_B) shifts. The size and shape of Au nano-particles were determined by high-resolution medium energy ion scattering combined with scanning electron microscopy of a field emission type. The shape of Au nano-particles is well approximated by a partial sphere with diameter d and height h. It is found that the E_B shift is well expressed as number of atoms per particle (n_A) and independent of support species. The E_B shift changes dramatically at a critical n_A value of ∼70 atoms, where metal-nonmetal transition takes place. In the nonmetal region, the E_B shift increases steeply almost exponentially with decreasing n_A and in contrast, gradually decreases with increasing n_A in the metallic region. The effect of the positive charge of an Au 4f vacancy created by photoemission is expressed by the relaxation time τ and the effective charge +αe when the photoelectron just leaves the Au particle surface (e: electron charge, α < 1).     

Mößbauereffekt in Eisenstilben und FeCl2·H2O

Using Mößbauer effect measurements in the temperature range between 3 °K and 310 °K the magnetic fields at the nucleus in iron-stilbene, FeCl₂·H₂O and FeCl₃ are determined to beH _T=0=(250±10) kOe, (252±18) kOe and (468±10) kOe; a Néel-temperature ofT _N=(23±1) °K is measured for iron-stilbene. The electric quadrupole splittings atT=0 °K for iron-stilbene and FeCl₂ ·H ₂ O, ΔE=(+2.52±0.02) mm/sec and (+2.50±0.05) mm/sec, yield electric field gradients at the iron nucleus ofq _z=+9.7·10¹⁷ V/cm² and +9.6·10¹⁷ V/cm², whereq _z⊥H; Debyetemperatures of θ=162 °K and 188 °K are obtained. The energy of the excited 3d-electron levels in iron-stilbene is estimated to Δ₁=309 cm^?1 and Δ₂=618cm^?1 as deduced from the temperature dependence ofΔE. In contrast to the suggestion ofEuler andWillstaedt bivalence of the iron in ironstilbene is found; its composition is shown to be 4(FeCl₂ ·H ₂O)·stilbene.     

Dynamic shielding of a charge in a metal

A discussion of the shielding of a charged particle in a current-carrying conductor is given that is based on the linearized Thomas-Fermi approximation. An expression for the force on a particle of charge q is obtained from which the value of the electric field E_c in the conductor may be found:

$\text{E}{}_{\mathrm{c}}\text{=}\text{lim}\text{q→0}\text{F}{}_{\mathrm{q}}\text{/q}$

It is shown that the force on the particle has the form $\text{F}{}_{\mathrm{q}}\text{= q}\text{E}{}_0\text{× (1 + γ(}\text{q}\text{e}\text{) + …}$ to second order in the charge q, where E₀ is the electric field at large distances from q, e is the charge of the carrier, and γ is a material-dependent constant. The shielding correction has the character of a “wind-force,” and the electric field in the conductor is given by Ec = E₀.     

The far-infrared spectrum of tetrahydrothiophene: The bend/twist vibrations and associated barriers

The far-infrared spectrum of tetrahydrothiophene is reinvestigated with a resolution of 0.12 cm^?1 in the region of 50–350 cm^?1. In addition to the bend transitions (ν_b) below 120 cm^?1 reported previously, a number of sequences revealed by the improved resolution are observed for the first time and assigned to transitions of 2ν_b, of the twist (ν_t), and of difference combinations (ν_t - ν_b). Simple one-dimensional modeling of the twist sequence, which is derived from a self-consistent bend-twist energy level diagram, with a quadratic-quartic Hamiltonian suggests a barrier to planarity on the order of 4250 cm^?1. A two-dimensional potential function in the dimensionless coordinates is found to be V(q_b, q_t) = ?249.6q_b² + 4.48q_b⁴ ? 215.5q_t² + 2.73q_t⁴ + 7.00q_b²q_t².     

Some detailed investigations of optically detected Ē(2 E) →4 A 2 cross relaxation in ruby

Cross relaxation betweenē(² E) and⁴ A ₂ states of Cr³⁺ in ruby at an applied external magnetic field ofH=5336 Oe was measured by monitoring the ¦? 1/2〉_ex→ ¦? 3/2〉_g optical transition in the temperature region of 1.6 to 4.2 °K. The chromium concentration varied from 2.9· 10^?4 to 4 · 10^?6 Cr³⁺/Al³⁺. With a concentration greater than 2 · 10^?5, the light intensity of the observed transition increases when cross relaxation takes place, while below this value it decreases. By measurement of the fluorescent intensity of one transition and simultaneously inducing EPR ground state transitions, we monitored the effect of trapping. Taking the value for trapping from fluorescence decay time measurements, we have used rate equations for calculating the actual change of excited state population when cross relaxation occurs. With this phenomenological model we are able to explain our experimental data. Finally some calculations for the effective spin temperature in theē(² E) state as a function of Cr³⁺ concentration as well as for various applied magnetic fields have been done.     

Shift of a Γ-X junction due to hydrostatic pressure

Hydrostatic pressure causes a shift of a Γ-X junction in the direction opposite to the band-gap gradient. The shift is of the order of 1μ/kbar in the samples investigated. From the shift and the band-gap gradient, the intervalley pressure coefficient (?/?P) (E_X–E_Γ) is estimated to be — 9·0^-6 eV/bar for the composition of Al_xGa_1-xAs corresponding to the Γ-X crossover.