Auger spectra by the Green's function method

Auger energies are calculated from the poles of the one-particle and particle—particle Green's functions. The theory is applied to the hydrogen fluoride molecule.     

Green's function calculations on the Auger spectra of CO

The Auger spectra of carbon monoxide have been calculated by the Green's function method and the unsolved assignment problems have been studied. Electron correlation plays an important role in all parts of the spectra. The results favour the assignment of the 250 eV peak in the C (KVV) spectrum as mainly 4σ¹5σ¹.     

He (I) and He (II) photoelectron spectra of ozone

The he I (21.2 eV) and He II (40.8 eV) photoelectron spectra of ozone have been recorded under high resolution. Ionization potentials are identified at 12.75 eV, 13.02 eV, 13.57 eV, and two broad bands are centered at 17.7 eV and 20.1 eV. The experimental results and the orbital assignment are not completely in accord with those given recently in the literature.     

Green's function calculations of ground-state correlation energies

A computationally convenient and numerically stable procedure is reported for the direct calculation of ground-state correlation energies employing one-particle Green's functions.     

He(I) and He(II) photoelectron spectra of some mixed sandwich compounds of titanium,zirconium and hafnium

The He(I) and He(II) photoelectron spectra are reported for two series of transition metal mixed sandwich complexes of general formula L_aML_b (M = Ti, L_a = η⁵-C₅H₅, η⁵-CH₃C₅H₄, η⁵-C₅(CH₃)₅; M = Zr, Hf, L_a = η⁵-C₅(CH₃)₅; L_b = η⁷-C₇H₇ (series I); M = Ti, L_a = η⁵-CH₃C₅H₄, η⁵-C₅(CH₃)₅; M = Zr, L_a = η⁵-C₅(CH₃)₅; L_b = η⁸-C₈H₈ (series II)). Assignments were made of the metal d, cyclopentadienyl and carbocyclic π orbitals on the basis of He(I)/He(II) intensity ratios and shift effects and by comparison with UP data for related compounds. For series I no influence of the central metal upon the IEs of the highest occupied molecular orbital e₂ was observed. The IE of the non-bonding metal d_z2 orbital of Ti or Zr (5.28 and 4.70 eV, respectively) in the complexes of series II (L_a = η⁵-C₅(CH₃)₅) is very low.     

Green's function semiclassical quantization of non-closed quasiperiodic classical trajectories

A semiclassical quantization procedure is introduced within the Green's function formalism for non-closed quasiperiodic trajectories which have previously defied quantization with this formalism. The results are interpreted in terms of the uncertainty principle and lead to conjectures concerning the semiclassical quantization of ergodic trajectories.     

Green's function calculations on the complete valence ionization spectra of HF,HCl, HBr AND HI

The ionization spectra of the entire valence region are calculated for HF, HCl, HBr and HI. For the two ionization processes of lowest energy the common molecular orbital picture of ionization applies, whereas this picture breaks down for ionization from the inner valence α-orbital. For HF and HCl basis set effects on the calculated outer-valence ionization energies are investigated and accurate values are computed using large basis sets. The calculated inner valence ionization spectra are compared with recent (e, 2e)-measurements.     

(He 1) photoelectron spectra of vinyl- and (1-dimethylaminovinyl)pyridines

The (He 1) photoelectron spectra of -, -, -vinyl, -, -, and -(1-dimethylvinyl)-pyridines, 1-dimethyl- and 1-diethylaminostyrenes were obtained and interpreted within the framework of the molecular orbital perturbation theory. In both pyridine derivative series, there is a regular increase in the ionization energy of the 1a ₂, C=C and n_en orbitals and decrease in the ionization energy of the 2b₁ orbitals in the order < < (inversion of orbitals 1a ₂ and 2b₁ is found for -vinylpyridine). The splitting of the energy levels of the heterocycle in dimethylaminovinylpyridines is less than in the corresponding vinyl derivatives, which indicates a weakening of the interaction between the aromatic (or heteroaromatic) ring and the enamine fragment extruding from the ring plane. The ionization energy of the unshared electron pair of the nitrogen atom of the pyridine ring for all the compounds except for -(1-dimethylaminovinyl)pyridine (which displays an ortho effect) is close to that for pyridine. The photoelectron spectral data are compared with the MO energies calculated by the MINDO/3 method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 103–108, January, 1985.     

Calculations on the helium isoelectronic sequence using Coulomb Green's function variables

Calculations on the ground states of the helium isoelectronic series are carried out using variational wavefunctions of the form ψ (x,y), in which x and y are the combinations r₁ + r₂ ± r₁₂ occurring in the Coulomb Green's function. The results for helium are the most accurate to date using a two-variable wavefunction accounting for 71.5% of the correlation energy.     

The absorption and circular dichroism bandshapes of chromophore aggregates as studied by a modified Green's function theory

A modified Green's function method is applied to calculating the aggregate bandshape whereby a decoupling approximation for vibrationally averaging the Green's function is used to include thermal and static effects as well in terms of the correction shift of the chromophore bandshape. The utility of the present method is shown by a sample calculation of the absorption and circular dichroism bandshapes of a model dimer.     

X-ray photoelectron spectra of ruthenium(II) phthalocyanines

Summary The Ru 3d_5/2 and 3p_3/2 x-ray photoelectron spectra of mono-and non-chlorinated ruthenium phthalocyanines were measured and the collected data on the core-level binding energies of ruthenium have been used to assess the oxidation state of the metal and the composition of the macrocyclic ligands.     

Photoionization cross sections: He I and He II photoelectron spectra of saturated three-membered rings

The relative band intensities in the He I and He II photoelectron spectra of cyclopropane, oxirane, and thirane are interpreted by means of a recent theoretical approach. For each compound, the assignment of the two bands in the 15–18 eV range derived from our intensity arguments is opposite to the sequence of the respective ab initio eigenvalues.     

Double-ionization auger satellites obtained by the green's function method

A three-particle Green's function approach is used to obtain triple ionization potentials and double-ionization Auger satellites. Electron correlation is included beyond reorganization. Transition energies and intensities are calculated for the hydrogen fluoride molecule. The assignment of the 629 eV structure to double-ionization satellites is confirmed.     

The surface activity of p-aminotriphenylmethane dyes in organic solvents - He(I) photoelectron spectra

At 0.23 M, the superficial layer of a solution of malachite green hydroxide or of brilliant green hydroxide in hydroxy-propionitrile consists entirely of the dye (as measured by He (I) photoelectron spectroscopy). This surface activity is weak or non-existent in the chloride and oxalate of malachite green, in some related dyes like brilliant green bisulphate and in the hydroxides and salts of both p-rosaniline and crystal violet.     

UV photoelectron spectra of some transition metal(II) acetylacetonates

The He(I) photoelectron spectra of acetylacetone (HAA) and its metallo complexes, M(II)(AA)₂ (M(II) = Mn, Co, Ni, Cu and Zn), have been measured. These spectra show characteristic metal-dependence, from which the assignment is made. The order of the orbital energy level, d > π₃ > n_? > n₊, holds for all the complexes reported here. The splitting of these orbitals is found to depend on the central metal ion specifically.     

The He(I) photoelectron spectra of OsO4, and RuO4

The photoelectron spectra of ruthenium tetroxide and osmium tetroxide excited by He(I) radiation are reported. From their interpretation it follows that the first two strong low energy transitions in the electronic absorption spectra of OsO₄, RuO₄, TcO^?₄, ReO^?₄, MoO^2?₄ and WO^2?₄ can be assigned to t₁ → 2e and 3t₂ → 2e respectively.