High Resolution Inner‐Shell Spectroscopy and ab initio CI Calculations on TiCl<sub>4</sub> and Isoelectronic Molecules.

Fronzoni, G.; Coreno, Marcello; Simone, Monica de; Franceschi, Pietro; Furlani, C.; Furlan, Sandra; Stener, Mauro; Decleva, P.

doi:10.1002/chin.200336002

Cited by 5 publications

(9 citation statements)

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“…The measurements were performed on the Gas Phase Photoemission beamline at the synchrotron radiation source Elettra, Trieste, Italy. Cross-sections were measured with a windowless, double absorption cell described elsewhere, which permits the absolute cross-section to be derived from the ion currents and minimizes errors due to stray light, higher order light, and saturation effects . The double cell method depends on achieving sufficient absorption for the currents in the two cells to be significantly different, so that the logarithm of the quotient of the currents reflects the change in cross-section.…”

Section: Methodsmentioning

confidence: 99%

Near Edge X-ray Absorption Spectra of Some Small Polyatomic Molecules

et al. 2003

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We report high resolution measurements of near edge X-ray absorption fine structure spectra (NEXAFS) at the carbon and oxygen K edges of the series of related organic molecules acetaldehyde, acetone, formic acid, methanol, dimethyl ether, and paraldehyde. The spectra are compared with previous measurements of these gases and formaldehyde and with theoretical calculations. Much more fine structure is resolved than previously, particularly at the carbon edge. The results are in good overall agreement with the theoretical predictions of Plashkevych et al. (Chem. Phys. 2000, 260, 11) that the methyl group spectrum is relatively independent of the functional groups to which it is bonded, as are the carbon and oxygen carbonyl group spectra. On the other hand, oxygen atoms in hydroxyl and ether groups are strongly influenced by neighboring atoms. All of the carbon edge spectra investigated show fine structure, and only in the case of acetone do the density of states and number of vibrational degrees of freedom begin to obscure fine detail. The term values of the strongest transitions to states of acetaldehyde and acetone at the C 1s and O 1s edges are in reasonable agreement with theoretical calculations. The splittings of the C 1s -1 3p(CH 3 ) and 3p(CO) Rydberg states due to the low symmetry of the molecules are 0.6-0.7 and 0.38 eV for both molecules, in good agreement with theory. Absolute values of the photoabsorption cross-section, where available in the literature, show moderate to very poor agreement with measured values.

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Section: Methodsmentioning

confidence: 99%

Near Edge X-ray Absorption Spectra of Some Small Polyatomic Molecules

et al. 2003

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“…Measurements were carried out on the undulator-based gas phase photoemission beamline at the "ELETTRA" synchrotron, Trieste 21 , using the ARPES chamber. 22 The monochromator was a VASGM (Variable Angle Spherical Grating Monochromator), working with four gratings to cover an incident photon energy range of 20 to 1200 eV, with a photon energy resolution DE/E ≤ 10 -4 . PE spectra were normalized to the incident photon flux using the signal from a calibrated photodiode (IRD, Inc.).…”

Section: Photoelectron (Pe) Spectramentioning

confidence: 99%

A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3+

Coates

Coreno²,

Simone

et al. 2009

Dalton Trans.

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The electronic states of CeCp(3)(+) have been studied experimentally by variable photon energy photoelectron spectroscopy, and computationally using multi-configurational ab initio methods. Relative partial photoionisation cross section and branching ratio data are presented to confirm our previous conclusion that bands A and D in the valence photoelectron spectrum, despite their 3.2 eV separation, are produced by ionization of the single 4f electron of CeCp(3) [M. Coreno, M. de Simone, J. C. Green, N. Kaltsoyannis, N. Narband and A. Sella, Chem. Phys. Lett., 432, 2006, 17]. The origin of this effect is probed using the CASSCF/CASPT2 approach. While configurations based on the canonical CASSCF orbitals are found to be an unreliable description of the ground and excited states of CeCp(3)(+), the state-specific natural orbitals and their occupations yield greater insight, allowing us to characterize ion states in terms of the presence or otherwise of a Ce 4f-localised electron. Neither the CeCp(3)(+) ground state (assigned to band A), and two excited states ((1)A' and (1)A'', associated with band D), possess such a metal-based electron, as expected of f ionization. The (1)A' and (1)A'' states differ from the ground state in having a significant Ce 5d population, arising from Cp --> Ce charge transfer, which accompanies f ionization, and which is responsible for the energetic separation of bands A and D in the valence photoelectron spectrum.

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“…The PE spectral measurements were carried out on the undulator based gas-phase photoemission beamline at ELETTRA, Trieste, using the angle resolved photoelectron spectrometer (ARPES) chamber and an ionization cell . The monochromator is a VASGM (variable angle spherical grating monochromator), working with four gratings to cover the energy 15−1000 eV, with a mean energy resolution Δ E / E ≥ 10.000.…”

Section: Methodsmentioning

confidence: 99%

Electronic Structure of ReO₃Me by Variable Photon Energy Photoelectron Spectroscopy, Absorption Spectroscopy and Density Functional Calculations

et al. 2003

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Valence photoelectron (PE) spectra have been measured for ReO(3)Me using a synchrotron source for photon energies ranging between 20 and 110 eV. Derived branching ratios (BR) and relative partial photoionization cross sections (RPPICS) are interpreted in the context of a bonding model calculated using density functional theory (DFT). Agreement between calculated and observed ionization energies (IE) is excellent. The 5d character of the orbitals correlates with the 5p --> 5d resonances of the associated RPPICS; these resonances commence around 47 eV. Bands with 5d character also show a RPPICS maximum at 35 eV. The RPPICS associated with the totally symmetric 4a(1) orbital, which has s-like character, shows an additional shape resonance with an onset of 43 eV. The PE spectrum of the inner valence and core region measured with photon energies of 108 and 210 eV shows ionization associated with C 2s, O 2s, and Re 4f and 5p electrons. Absorption spectra measured in the region of the O1s edge showed structure assignable to excitation to the low lying empty "d" orbitals of this d(0) molecule. The separation of the absorption bands corresponded with the calculated orbital splitting and their intensity with the calculated O 2p character. Broad bands associated with Re 4d absorption were assigned to (2)D(5/2) and (2)D(3/2) hole states. Structure was observed associated with the C1s edge but instrumental factors prevented firm assignment. At the Re 5p edge, structure was observed on the (2)P(3/2) absorption band resulting from excitation to the empty "d" levels. The intensity ratios differed from that of the O 1s edge structure but were in good agreement with the calculated 5d character of these orbitals. An absorption was observed at 45 eV, which, in the light of the resonance in the 4a(1) RPPICS, is assigned to a 4a(1) --> ne, na(2) transition. The electronic structure established for ReO(3)Me differs substantially from that of TiCl(3)Me and accounts for the difference in chemical behavior found for the two complexes.

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High Resolution Inner‐Shell Spectroscopy and ab initio CI Calculations on TiCl₄ and Isoelectronic Molecules.

Cited by 5 publications

References 1 publication

Near Edge X-ray Absorption Spectra of Some Small Polyatomic Molecules

Near Edge X-ray Absorption Spectra of Some Small Polyatomic Molecules

A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3+

Electronic Structure of ReO₃Me by Variable Photon Energy Photoelectron Spectroscopy, Absorption Spectroscopy and Density Functional Calculations

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High Resolution Inner‐Shell Spectroscopy and ab initio CI Calculations on TiCl4 and Isoelectronic Molecules.

Cited by 5 publications

References 1 publication

Near Edge X-ray Absorption Spectra of Some Small Polyatomic Molecules

Near Edge X-ray Absorption Spectra of Some Small Polyatomic Molecules

A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3+

Electronic Structure of ReO3Me by Variable Photon Energy Photoelectron Spectroscopy, Absorption Spectroscopy and Density Functional Calculations

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Product

Resources

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High Resolution Inner‐Shell Spectroscopy and ab initio CI Calculations on TiCl₄ and Isoelectronic Molecules.

Electronic Structure of ReO₃Me by Variable Photon Energy Photoelectron Spectroscopy, Absorption Spectroscopy and Density Functional Calculations