The partnership of gas-phase core and valence photoelectron spectroscopy

Jolly, William L.

doi:10.1021/ar00094a002

Cited by 24 publications

(5 citation statements)

References 38 publications

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“…Several investigators have obtained C Is energies of organometallic complexes15"18 and have related these results to the structure and bonding of these molecules. 19,20 In order to assess the ability of the present calculations to reproduce correct relative C Is ionization energies, we performed calculations on chromium-benzene organometallic complexes.15,18 A comparison of experimental and theoretical results is presented in Table V. One interesting result seen in Table V is that the calculated C Is shift is larger for the mono(benzene)chromium complex, Cr(C6H6), than it is for the bis(benzene)chromium complex, Cr(C6-H6)2.…”

Section: Methodsmentioning

confidence: 99%

A theoretical study of the bonding and XPS spectra of chromium interacting with a polyimide model compound

Rossi¹,

Sanda²,

Silverman³

et al. 1987

Organometallics

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Molecular orbital calculations have been performed on a complex of chromium with N,N'-diphenylpyromellitimide, a compound structurally similar to the PMDA part of the PMDA-ODA polyimide repeat unit. The PMDA/Cr complex investigated involving chromium located above the central benzene ring is one of several possible complexes formed under the experimental conditions of clean surfaces and ultrahigh vacuum.The calculated C Is core levels, together with Koopmans' approximation, provide a reasonable fit to the carbon Is XPS data, if it is assumed that the observed spectrum reflects a portion of both reacted and unreacted molecular species.

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Section: Methodsmentioning

confidence: 99%

A theoretical study of the bonding and XPS spectra of chromium interacting with a polyimide model compound

Rossi¹,

Sanda²,

Silverman³

et al. 1987

Organometallics

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Section: Correlation Of Core and Valence Ionization Energy Shiftsmentioning

confidence: 99%

“…The principles of this analysis were originally formulated by William L. Jolly − and are illustrated schematically for the bdt S π+ FOE in Figure . Jolly found empirically that the ionization energy shift of a valence orbital localized on an atom, ΔIE V , was 0.80 ± 0.07 of the ionization energy shift of the core orbital on that atom, ΔIE C . − Deviations of ΔIE V from 0.80ΔIE C were accounted for by the overlap of valence orbitals in bonding and antibonding interactions. Here we extend the concept of a localized orbital ionization potential (termed LOIP in Jolly’s analysis), in which the orbital is localized on a single atom, to the concept of a fragment orbital energy (FOE), in which the orbital may be delocalized within a fragment of a complex.…”

Section: Correlation Of Core and Valence Ionization Energy Shiftsmentioning

confidence: 99%

Metal–Sulfur Valence Orbital Interaction Energies in Metal–Dithiolene Complexes: Determination of Charge and Overlap Interaction Energies by Comparison of Core and Valence Ionization Energy Shifts

et al. 2011

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The electronic interactions between metals and dithiolenes are important in the biological processes of many metalloenzymes as well as in diverse chemical and material applications. Of special note is the ability of the dithiolene ligand to support metal centers in multiple coordination environments and oxidation states. To better understand the nature of metal-dithiolene electronic interactions, new capabilities in gas-phase core photoelectron spectroscopy for molecules with high sublimation temperatures have been developed and applied to a series of molecules of the type Cp2M(bdt) (Cp = η5-cyclopentadienyl, M = Ti, V, Mo, and bdt = benzenedithiolato). Comparison of the gas-phase core and valence ionization energy shifts provides a unique quantitative energy measure of valence orbital overlap interactions between the metal and sulfur orbitals that is separated from the effects of charge redistribution. The results explain the large amount of sulfur character in the redox-active orbitals and the ‘leveling’ of oxidation state energies in metal-dithiolene systems. The experimentally-determined orbital interaction energies reveal a previously unidentified overlap interaction of the predominantly sulfur HOMO of the bdt ligand with filled π orbitals of the Cp ligands, suggesting that direct dithiolene interactions with other ligands bound to the metal could be significant for other metal-dithiolene systems in chemistry and biology.

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“…In the early 1980s, Jolly and co-workers developed an approach to studying the bonding character of MOs, using the chemical shift information of both core and valence levels of related compounds. 41 The basic principle of Jolly's approach is that the appropriately chosen core BEs can be used to subtract the contributions due to electrostatic potential (atomic charges) and relaxation energy from valence ionization potentials. It is then possible to quantify the bonding or antibonding character of molecular orbitals by using only experimental data.…”

Section: 2b the Assignments Of Re(co)mentioning

confidence: 99%

Variable-Energy Photoelectron Spectroscopy of Substituted Rhenium and Manganese Pentacarbonyls: Molecular Orbital Assignments and the Interatomic Resonant Effect

Bancroft

Tan

2000

Inorg. Chem.

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High-resolution variable-energy photoelectron spectra of M(CO)5X [M = Re, X = Re(CO)5, Cl, Br, and I; and M = Mn, X = Mn(CO)5 and Br] are reported. Tunable synchrotron radiation is used to distinguish the Re 5d and Br 4p orbital based peaks for the controversial Re(CO)5Br. Our results provide firm molecular orbital assignments for all of these molecules. The valence orbital in the ordering of ionization energies for M(CO)5Cl (M = Mn and Re) and Mn(CO)5Br is a 1(M-X) > e(X) > b2(M) > e(M); but for M(CO)5I (M = Mn and Re) and Re(CO)5Br the ordering is a1(M-X) > e(M) > b2(M) > e(X). The crossover of the HOMO in the Re molecules due to the change in the halogen electronegativities occurs at Re(CO)5Br. The metal np-->nd resonance is observed for all of these molecules. For molecules like M2(CO)10 (M = Re and Mn) and Mn(CO)5Br, the observation of this np-->nd resonance is useful in assigning the metal nd based orbitals in their valence level spectra. However, for molecules like Re(CO)5X (X = Br and Cl), a np-->nd type resonance is observed on bands arising from both Re 5d and halogen mp based orbitals. This new resonant effect on the ligand-based orbitals is shown to be mainly due to the interatomic resonant effect. The core and valence level chemical shifts of these compounds are treated using Jolly's approach to confirm the assignments for the valence level spectra of some of these molecules. The high-resolution inner valence and core level spectra of these compounds are reported. Broadening of Re 4f, Br 3d, and I 4d core level spectra is discussed. The Auger peaks are observed in the high-resolution, high-intensity Br 3d of Re(CO)5Br and I 4d of Re(CO)5I spectra.

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The partnership of gas-phase core and valence photoelectron spectroscopy

Cited by 24 publications

References 38 publications

A theoretical study of the bonding and XPS spectra of chromium interacting with a polyimide model compound

A theoretical study of the bonding and XPS spectra of chromium interacting with a polyimide model compound

Metal–Sulfur Valence Orbital Interaction Energies in Metal–Dithiolene Complexes: Determination of Charge and Overlap Interaction Energies by Comparison of Core and Valence Ionization Energy Shifts

Variable-Energy Photoelectron Spectroscopy of Substituted Rhenium and Manganese Pentacarbonyls: Molecular Orbital Assignments and the Interatomic Resonant Effect

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