X-ray and UV photoelectron-spectroscopic studies of pyridine adsorbed on evaporated nickel and palladium in the temperature range 140–385 k

The states of pyridine adsorbed on evaporated nickel and palladium films have been investigated as a function of temperature in the range 140–385 K by means of X-ray and UV photoelectron spectroscopy. At ～ 140 K, pyridine “N-bonded” on the metal surfaces gives C 1s and N 1s peaks whose binding energies are very close to those for condensed pyridine and “N-bonded” pyridine on pre-oxidized nickel. The high-lying valence orbitals, 2b₁ (π) and 1a₂ (π) + 7a₁ (n), of pyridine show shifts similar to those for the “N-bonded” molecule on pre-oxidized nickel. At ～ 290 K, “π-bonded” pyridine shows large shifts in the C 1s and N 1s peaks and in the high-lying valence orbitals, as observed for “π-bonded” benzene on nickel. The assignments of the adsorbed states are supported by work-function change data. A large proportion of pyridine converts from the “N-bonded” to the “π-bonded” form between 220 and 290 K. Formation of “α-pyridyl” is suggested at ～ 375 K on nickel.     

Thermal activation measurement of positron binding energies at surfaces

The formation of positronium by low-energy positrons incident on “clean” metal surfaces is thermally activated by increasing temperature. The activation energy E_a has been measured for a number of surfaces. E_a is understood as the energy required to form positronium (binding energy 1/2Ry) from positrons bound at the surface by an energy E_b, E_a = E_b+φ_-? 1/2Ry, where φ_- is the electron work function. Representative values of E_b derived are Al(100):3.03(5) eV; Al(110):2.92(4) eV; Cu(111):2.80(5) eV.     

Electronic structure of solid pyridine and pyridine adsorbed on polycrystalline silver

The electronic structure of the valence bands of polycrystalline films of pyridine (C₅H₅N), including all valence levels extending from initial energies of 4 down to 30 eV (E_VAC = 0), has been determined from photoelectron energy distribution measurements for photon energies 20eV ? hν ? 170 eV, using synchrotron radiation. The valence bands showing a one-to-one correspondence to the gas phase, a rigid relaxation shift of δe_r = 0.3 eV for the vertical binding energies, and a considerable solid state broadening (? 0.5 eV) are assigned in comparison to recent MO calculations. By tuning the photon energy and thereby achieving high surface sensitivity for hν around 45 eV, we have also studied pyridine adsorbed at 120 K (6 Langmuir) on in situ prepared polycrystalline Ag-substrates. Thus, we were able to study in detail the surface electronic structure in the range of the Ag 4d bands. Due to a strong mixing of substrate 4d and pyridine 2b₁ (π), 1a₂ (π) and 7a₁ (n) energy levels, the surface electronic structure is strongly modified in the upper part of the 4d bands, and a strong and sharp (0.4 eV FWHM) surface resonance at an energy of 3.7 e V below E^AG_F is observed, which we attribute to a 4d-7a₁ (n) bonding of the nitrogen lone-pair orbital.     

Shallow impurity states and the free exciton binding energy in gallium phosphide

A new set of donor and acceptor ionization energies in GaP is deduced from photoexcitation spectra. Energy spectrum of donor states confirms an existence of the “camel's back” with a conduction band minima displacement ≈ 0.08(2π/a) from the X, and the corresponding energy shift ≈ 3meV. The free exciton binding energy in GaP is correctly determined: E_ex = 21 ± 2 meV.     

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.     

Zur Theorie der Vorwärtsasymmetrie bei der Photospaltung des Deuterons

The forward asymmetry in the differential cross section for the photo disintegration of the deuteron has been calculated on the basis of a phenomenological theory for energies up to 80 MeV. The formulas for this asymmetry, which come from theE1-E2-andM1-M2-interference, are given, assuming the validity ofSiegert's theorem. TheE2-andM2-amplitudes are calculated approximately, using the Hulthén wavefunction with a 4% D-state admixture for the ground state and scattered waves determined by the phase shifts given by Marshak for the final states. The contribution of theM1-M2-interference turns out to be unimportant for the asymmetry, theE1-E2-interference giving the main effect. In the differential cross section,dσ/dΩ=a + b sin ² ? + c cos ? + d cos ? sin ² ?, we have obtained a very low value forc and the ratioc/d is approximately equal toa/3b. This is in contradiction to the assumptionc/d=a/b made in the previous analysis of the experimental data. This ratio seems to be insensitive to the value of the D-state admixture. For the lover energiesE _γ=10 MeV andE _γ=20 MeV the theoretical values for “d” are in agreement with the experimental ones. For the energies 54 and 80 MeV we have made a comparison of the theoretical differential cross sectiondσ/dΩ, taking into account the values for “a” and “b”, obtained in a former work ie, with the measureddσ/dΩ.     

Point defects in polycrystalline calcium sulphide

Polycrystalline CaS has been prepared by reduction of CaSO₄ in H₂ and H₂S at 1000°C. Such preparation is conducive to the formation of point defects, which have been investigated by the electron paramagnetic resonance method (EPR). All CaS samples reveal the presence of ultraviolet sensitive EPR signals “a₀” and “b₀” of g values 1.9998 and 2.0018, respectively. We had earlier reported the “a₀” signal, which shows thermal quenching. Its intensity increases with decreasing temperature and reaches a near saturation below about -90°C. “b₀” shows a complex variation with temperature. Both these signals appear to be due to sulphur vacancies. Prolonged X-ray irradiation removes these signals and produces F⁺ signals.     

Low energy photoelectron spectroscopy of solids. Aspects of experimental methodology concerning metals and insulators

Both He(I) and He(II) ultraviolet photoelectron spectra (UPS) for metals (Ag, Au) and thin solid films of organic (anthracene) and inorganic compounds (LiF, LiCl, LiBr, LiI, NaF, NACl, Li₂SO₄, NaOH) are presented. The results of measurements on two different spectrometers have shown that both the bias voltage, V_b, applied to the solid sample, and the angle of incidence, Ø, of the photon beam with the sample are crucial to the accurate determination of the work function (metals) and binding energies (insulators). The true binding energy of a band in the UPS with respect to the vacuum level, E_b^vac, is defined as the minimum value of (hv - ΔE), where ΔE is the energy difference between the threshold of the SEED, E_T, and the band maximum. ΔE is maximized at low values of ø and of V_b. The intensity of photoelectron emission (signal) increases with both ø (2–30°) and V_b (5–20 V). It is recommended that the variation of ΔE with both ø and V_b should be observed in any determination of E_B^vac.     

Multiphoton Spectroscopy

Abstract

Absorption and cmission spectroscopies, which are widely utilized by chemists, can be classified as one–photon spectroscopy. A molecule is excited from its ground state of energy E₀ to thc excited state of E_e by the absorption of one photon of frequency given by the Bohr's condition (hω=E_e-E₀). The reverse transition is accompanied by the emission of one photon of the same frcquency. Therefore, the molecular state energies can be directly obtained by the photon encrgies absorbed or emitted. Infrared, microwave, electronic absorption, and emission spectroscopies belong to this category of one–photon spectroscopy.     

Optical anisotropy of orthorhombic InS

The optical anisotropy of InS single crystals in the range of photon energy from 1.8 to 3.5 eV has been studied by absorption, electroreflectance and wavelength-derivative reflectance measurements. These systematic optical measurements for the polarizations, E//a and E//b, have revealed that the transition at the fundamental absorption edge of InS is allowed for E//b, and there exist three distinct doublet transitions having different selection rules in the photon energy region from 2 to 3.5 eV; Bo and B^'₀doublet allowed only for E//b, A₀ and A^'₀ allowed only for E//a, and E₁ and E^'₁ allowed for both polarizations. The observed results are discussed based on the anisotropic nature of two chemical bonds in InS, cation-cation and cation-anion.     

Imidazoline biradical spin labels with EPR spectral sensitivity to the local concentration of protons

EPR spectral sensitivity of the three biradicals of imidazoline and imidazolidine types to the local concentration of protons (pH) in aqueous solutions has been studied. Significant increase ing-factor (Δg ≈ 0.0002) and decrease in hyperfine interaction constant (Δa_N = 0.8?1.2 G) upon the protonation of atom N-3 of the radical heterocycle were observed. The pH dependence of a_N andg- factor is described by conventional titration curve with one or two pK values. The latter case was explained by nonindependent protonation of two monoradical fragments closely located in the biradical structure. EPR spectra of protonated and deprotonated forms of the biradicals have significantly different intensities of “biradical” components, I_b, reflecting changes in spin exchange interaction. It has been found that activation energy of spin exchange, E_a, estimated from temperature dependence of I_b in glycerol/water solution is lower for the biradical conformation with larger I_b. This is in agreement with main contribution of direct collisions of monoradical fragments in spin exchange interaction so larger value of I_b corresponds to the conformation with less spatial restrictions for the motion of monoradical fragments (lower E_a). The potential use of the pH-sensitive biradicals as spin labels is discussed.     

EXAFS measurements of bond-stretching force constants in arsenic and arsenic compounds

The Einstein frequency ν_E obtained from temperature-dependent EXAFS measurements for the bond between an arsenic atom and a nearest neighbor in arsenic and certain arsenic halides and chalcogenides is considered. It is shown theoretically that in these materials ν_E should be approximately equal to the “natural” frequency of the bond, and hence that ν_E² is proportional to the bond-stretching force constant ⨍_r. Experimental EXAFS measurements on crystalline (c-) AsBr₃ and AsI₃, glassy (g-) As₂S₃ and As₂Se₃, and amorphous (a-) As yield force constants in reasonable agreement with those obtained from Raman and infrared studies.     

The prediction of core-level binding-energy shifts from CNDO molecular orbitals

A theory is described for calculating core-level binding-energy shifts with potential models that employ “intermediate-level” molecular-orbital wave functions. The relaxation-energy term in atomic core-level binding energies is considered first. The ground-state potential model (GPM) and relaxation-potential model (RPM) are developed for calculating core-level binding energy shifts in molecules from CNDO wavefunctions. It is shown that neglect of certain two- and three-center integrals in these models limits their accuracy when unlike molecules are compared. The models are modified by calculating r^?1 integrals, to be sensitive to bond directions of p orbitals. The pp′ modification, in which a subset of the neglected integrals is retained to recover invariance to coordinate transformations, is thereby necessitated. The GPM approach yields shifts in very good agreement with experiment when comparisons are restricted to similar molecules. The RPM version gives better agreement especially over wider classes of molecules. It also provides relaxation energies V_R that can be combined with ab initio orbital energies to give binding energies. Several applications of these potential models are discussed.     

Relative partial photoionization cross-sections and photoelectron branching ratios of ethylene

Relative partial photoionization cross-sections and photoelectron branching ratios of the valence bands (~10–25 eV binding energy) of ethylene are reported over the photon energy ranges 18–100 eV and 21–100 eV, respectively. The four lowest ionization energy bands (1b⁻¹_1u, 1b⁻¹_1g, 3a⁻¹_g, and 1b⁻¹_2u) show monotonic cross-section decreases with photon energy from 33 eV, the 1b⁻¹_1u CC π band showing the least rapid decline. In contrast, the 2b⁻¹_3u and 2a⁻¹_g bands show almost constant cross-sections up to ~50 eV photon energy, followed by similar, although slower, monotonic decreases. This is attributed to the substantial carbon 2s character of the 2b_3u and 2a_g orbitais. The cross-section behaviour of all bands is interpreted with the aid of SCF-LCAO-MO calculations on the neutral molecule using the Gaussian-80 series of programs.     

Influence of one CO molecule on structural and electronic properties of monatomic Cu chain

By using first-principles calculations, we have systematically investigated the structural and electronic properties of an infinite linear monatomic Cu chain with an adsorbed CO molecule. We find that the bridge geometry is energeticabsally favored not only when the Cu–Cu bond below the molecule is unstretched, but also for a wide range of d_Cu–Cu up to about 4.20 Å, while the substitutional geometry is favored only in the hyperstretched situation d_Cu–Cu>4.80 Å. Charge density differences point out the electron transfer is from the Cu atoms to the adsorbed CO molecule. The binding mechanism of CO to Cu chain can be described by the Blyholder’s model, in terms of σ-donation of electron density from the nonbonding CO-5σ orbital into empty metal orbitals and π-backdonation from the occupied metal d orbitals to empty CO-2π^⁎ orbital. The donation/backdonation process leads to the formation of bonding/antibonding pairs, 5σ_b/5σ_a and 2π_b^⁎/2π_a^⁎, with the 5σ_a lying above E_f and the 2π_b^⁎ below E_f.     

How chaotic is a state of a quantum system?

A concept related to the entropy is studied. Let A and B be two density matrices, with eigenvalues a₁, a₂,… and b₁, b₂,…, arranged in decreasing order and repeated according to multiplicity. Then A is said to be “more mixed”, or “more chaotic”, than B, if a₁?b₁, a₁+a₂?b₁+b₂,…,a₁+…+a_m?b₁+…+b_m,…; It turns out that if A is more mixed than B, then the entropy of A is larger than the entropy of B. However, more generally, let v be an arbitrary concave function, ?0, and vanishing at 0. Then, if A is more mixed than B, trv(A)?trv(B). It is shown that also the converse is true. Furthermore, a variety of other characterizations of the relation “A is more mixed than B” is obtained, and several applications to quantum statistical mechanics are given.     

Photon production in heavy-ion collisions at SPS energies

Single photon spectra in heavy-ion collisions at SPS energies are studied in the relativistic transport model that incorporates self-consistently the change of hadron masses in dense matter. We separate the total photon spectrum into “background” arising from the radiative decays of π⁰ and η mesons, and the “thermal” one from other sources. For the latter we include contributions from radiative decays of ρ, ω, η′, and a₁, radiative decays of baryon resonances, as well as two-body processes such as ππ → ργ and πρ → πγ. It is found that more than 95% of all photons come from the decays of π⁰ and η mesons, while the thermal photons account for less than 5% of the total photon yield. The thermal photon spectra in our calculations with either free or in-medium meson masses do not exceed the upper bound set by the experimental measurement of the WA80 Collaboration.     

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.     

Geometries, stabilities and electronic properties of small Nb-doped gallium clusters: A density functional theory study

The host Ga_n+1 and doped Ga_nNb (n=1-9) clusters with several spin configurations have been systematically investigated by a relativistic density functional theory (DFT) with the generalized gradient approximation. The optimized equilibrium geometries tend to prefer the close-packed configurations for small Nb-doped gallium clusters up to n=9. The average binding energies per atom (E_b/atom), second-order differences of total energies (Δ₂E), fragmentation energies (E_f) and HOMO-LUMO gaps of Ga_n+1 and Ga_nNb (n=1-9) clusters are studied. The results indicate the doping of Nb atom in gallium clusters improves the chemical activities. In particular, the clusters with sizes of Ga₄Nb and Ga₇Nb are found to be more stable with respect to their respective neighbors. Our calculated vertical ionization potentials (VIPs) exhibit an obvious oscillating behavior with the cluster size increasing, except for Ga₃ and Ga₄Nb, suggesting the Ga₃, Ga₅, Ga₇, GaNb, Ga₃Nb, Ga₆Nb and Ga₈Nb clusters corresponding to the high VIPs. In the case of vertical electron affinities (VEAs) and chemical hardness η, VEAs are slightly increasing whereas chemical hardness η decreasing as Ga_nNb cluster size increases. Besides, the doping of Nb atom also brings the decrease as the cluster sizes increases for atomic spin magnetic moments (μ_b).