Variable-Energy Photoelectron Spectroscopy of (eta(5)-C(5)H(5))NiNO: Molecular Orbital Assignment and Xalpha-SW Calculations

Variable-energy valence and inner-valence photoelectron spectra have been recorded for the CpNiNO complex (Cp = eta(5)-C(5)H(5)) between 21.2 and 100 eV, using He I radiation and synchrotron radiation. The ground state electronic structure has been calculated by using the Xalpha-SW method. Photoionization cross sections (sigma) have also been calculated for the valence ionizations using the Xalpha-SW method. The theoretical branching ratios (sigma(i)/ summation operatorsigma) have been compared with the observed branching ratios (A(i)()/ summation operatorA) between 21.2 and 100 eV. The assignment of the photoelectron spectrum based on the analysis of intensity variations and width of vibrational peaks is consistent with the ion state orbital ordering 5e(1)(1) < 7a(1)(2) < 3e(2)(3) < 4e(1)(4) (band numbers are in parentheses) and is inconsistent with another recently proposed ordering 5e(1)(1), 5e(1)(2) < 7a(1), 3e(2)(3) < 4e(1)(4), which takes the 5e(1) vibronic effects into consideration. The experimental branching ratio results indicate a Ni 3p resonance effect around 75 eV in the photoionization process. The inner-valence spectrum has also been assigned with the aid of the Xalpha-SW calculations.     

The sign of the Co quadrupole splitting in Co(III) compounds,and the magnitude of the Fe quadrupole moment

Using the partial quadrupole splitting values (PQS) for ligands such as Cl⁻, CN⁻ and NH₃ derived from Mössbauer spectra of Fe(II) low spin compounds, the sign of V_zz is obtained for (e²qQ)_Co in isoelectronic compounds of Co(III) low spin. The predicted signs of V_zz are: trans- [Co(NH₃)₄Cl₂]⁺, positive; [Co(NH₃)₅Cl]⁺⁺, positive, and [Co(NH₃)₅CN]⁺⁺, negative. A value of the ⁵⁷Fe quadrupole moment of 0.16 ± 0.03 has been determined by comparing the observed e²qQ values for the above Co(III) compounds with these calculated from PQS values for the corresponding hypothetical Fe(II) compounds.     

Synthesis and reduction of some 1H-2,1,3-benzothiadiazin-4(3H) one 2,2-dioxides

Several 2,1,3-benzothiadiazin-4(3H) one 2,2-dioxides were synthesized as possible sweetening agents by reacting sulfamoyl chloride with various anthranilic acid derivatives. The isolation of 1-methyl-4-methoxy-2,1,3-benzothiadiazine 2,2-dioxide and preparation of 3,4-dihydro-2,1,3-benzothiadiazine 2,2-dioxide is also reported.     

Photoemission studies of the outer core d level linewidths in Pb, In and Sn compounds using synchrotron radiation

Using synchrotron radiation as the photon source, high resolution electron spectra are reported for the outermost core d levels in Pb, Sn and In me     

An ESCA study of Sn organometallic compounds: Solid state broadening effects

X-ray photoelectron spectra have been recorded for a number of solid and gaseous organotin compounds. Solid-state charging effects (such as differential charge broadening) can be large, though we have almost eliminated them by subliming very thin films onto platinum metal. In this way, we have obtained solid-state Sn 3d line widths that are within 10% of the analogous gas-phase values. The quality and reproducibility of the solid-state spectra likewise approach those of gases.The general correlation between ESCA Sn 3d line widths and Mössbauer quadrupole splittings indicates that the broadening of the Sn 3d lines is due to crystal-field splitting from the C₂⁰ term (the quadrupole term) in the crystal-field expansion. There is a general correlation between ESCA binding energies and Mössbauer isomer shifts for the solids.     

Charged particle oscillator and hollow cathode He(II) lamps for high resolution photoelectron studies: C 2 s spectrum of CH 4 and Hg 5 d5/2 spectrum of (CH 3) 2Hg

Charged particle oscillator and hollow cathode He discharge lamps are described, and the performances of the two lamps in the same spectrometer are compared. Both lamps give high percentages of He(II) radiation, but the hollow cathode lamp gives higher overall He(I) and He(II) intensifies and has greater long term stability. The observed resolution for He(II) studies (～ 25 meV) is the same for both lamps. The C 2 s spectrum of CH ₄ and the Hg 5 d_5/2 spectrum of (CH ₃) ₂Hg demonstrate the performance of the hollow cathode lamp. In the CH ₄ spectrum, a vibrational progression is observed, and attributed to the totally symmetric stretching mode. The linewidth of individual components increases at higher binding energy. The high resolution of the (CH ₃) ₂Hg spectrum enables us to identify additional peaks not previously seen in this spectrum. The Hg 5 d orbital energy-ordering for Me ₂Hg is reassigned.     

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