Energy splitting of core electron levels in paramagnetic molecules

Hedman, J.; Hedén, Per Filip; Nordling, C.; Siegbahn, Kai

doi:10.1016/0375-9601(69)90801-9

Cited by 76 publications

(24 citation statements)

References 6 publications

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“…We note that slight changes in peak intensities were observed at different positions of the same sample as well as at different samples, in accordance with the relatively large standard deviations of the film thicknesses. The peak positions were in the range of 688.7~688.8 eV, which is a few hundred millielectron-volts less than those of the corresponding bulk IL spectra (vertical dotted lines, see Figure S3), as observed in our previous study of IL thin films on Au (111). 45 This tendency has already been reported by Steinrück and coworkers for the C 1s and N 1s peaks of the same and similar ILs on Au (111) and Ni (111), and it was attributed to the initial-state effect (IL bonding to the substrate) and/or the final-state effect (efficient core hole screening by the substrate) of the photoelectron excitation depending on the IL-film thickness.…”

Section: Methodsmentioning

confidence: 84%

Electronic-State Changes of Ferrocene-Terminated Self-Assembled Monolayers Induced by Molecularly Thin Ionic Liquid Layers: A Combined Atomic Force Microscopy, X-ray Photoelectron Spectroscopy, and Ultraviolet Photoelectron Spectroscopy Study

et al. 2015

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Ferrocene-terminated self-assembled monolayers (SAMs) have been studied in the last quarter-century to determine the relationship between their electrochemical properties and microscopic structures as a prototypical chemically modified electrode. Although electronic structures are directly related to the electrochemical properties, knowledge of such a relation concerning ferrocene-terminated SAMs is extremely limited. In this study, we deposited a small amount of ionic liquid onto three types of ferrocene-terminated SAMs possessing different ionization energies and performed X-ray and ultraviolet photoelectron spectroscopies to elucidate the changes in the electronic structure resulting from the adsorption of the ionic liquid.For a low-ionization-energy system, spontaneous oxidation of the ferrocene moieties occurred while their electrochemical activities were retained; for other systems, only minor changes were observed. This result indicates that the interaction between the ionic liquid and ferroceneterminated SAMs facilitates electron transfer when the energy difference between the highestoccupied molecular orbital of the ferrocene moieties and the Fermi level of the electrode becomes small.

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Section: Methodsmentioning

confidence: 84%

Electronic-State Changes of Ferrocene-Terminated Self-Assembled Monolayers Induced by Molecularly Thin Ionic Liquid Layers: A Combined Atomic Force Microscopy, X-ray Photoelectron Spectroscopy, and Ultraviolet Photoelectron Spectroscopy Study

et al. 2015

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“…Another core-level effect that was observed very early on is multiplet splittings in core-level emission from systems with unfilled valence shells [28,29]. The core subshell from which emission occurs can couple its spin and orbital angular momenta in different ways to the net spin and orbital angular momenta of the unfilled valence shells, resulting in more than one binding energy.…”

Section: Core-level Multiplet Splittingsmentioning

confidence: 97%

“…The first measurements of this type were by Siegbahn et al and are indicated in Fig. 3(a) for the O 2 , NO, and N 2 molecules [28], with the O 1s and N 1s binding energies for the paramagnetic molecules O 2 and NO 2 being split into two components due to the spin-dependent exchange interaction of the 1s electron remaining after photoemission with the net valence electron spin. Soon afterwards, such splittings were measured for the transition metal atom Mn in several compounds [29], as shown in Fig.…”

Section: Core-level Multiplet Splittingsmentioning

confidence: 98%

“…3. The first measurements of multiplet splittings due to the interaction of a core hole with unfilled valence shells, using Mg Ka at 1.25 keV for excitation: (a) in the paramagnetic molecules O 2 and NO, the O 1s and N 1s binding energies, respectively, are split into doublets, corresponding to high-spin and low-spin final ionic states [28] and (b) in several compounds of Mn, the Mn 3s level is split into a doublet due to the same type of interaction [29]. Splittings also exist for Mn 3p, but with a more complex form.…”

Section: Valence Bands and Angle-resolved Photoemissionmentioning

confidence: 99%

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X-ray photoelectron spectroscopy: From origins to future directions

Fadley

2009

Nuclear Instruments and Methods in Physics Research Section A:

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“…This phenomenon is termed multiplet SJ>litting of core-level binding energies. It was first reported in molecules by Hedman~ ~~., 10 12 . It has since been studied in transition metal salts 13 -lB and in the valence-band spectra of metal~.…”

Section: This Technique Is Capable Of Yielding Binding Energiesmentioning

confidence: 95%

Multiplet splitting in 1s hole states of molecules

Davis

Martin

Banna

et al. 1973

The Journal of Chemical Physics

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The binding energies of selected C, N, O, and F 1s electrons in six paramagnetic molecules were measured by x-ray photoemission. A splitting of 1.934(41) eV was observed in the N(1s) line of NF2, and several other splittings were remeasured or obtained by fitting asymmetric but unresolved lines. Use of the Mg Kα12 doublet profile in fitting improved the fits markedly. A multiplet hole theory was developed to predict the final-state multiplet splitting. It uses atomic exchange integrals, INDO calculations on an ``equivalent-core'' final state to obtain spin densities, and Van Vleck's Theorem to account correctly for multiplicity. It gives results in very good agreement with experiment, and it can be used for larger molecules. During photoemission spin density migrates away from the 1s hole in most cases, and electronic charge flows toward this hole, affecting both the 1s splitting and the 1s binding energy. The lower N(1s) binding energy in di-t -butylnitroxide than in NO arises from electron flow to nitrogen from the t -butyl group during photoemission. This inductive effect is closely related to the ease of substitution of nucleophilic groups in unimolecular reactions with tertiary alkyl halides, a phenomenon that must also be understood in terms of final- (or transition-) state properties, rather than simply in terms of the initial state. Inequivalent fluorines in N2F4 were identified by an unresolved doublet structure in the F(1s) peak.

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Energy splitting of core electron levels in paramagnetic molecules

Cited by 76 publications

References 6 publications

Electronic-State Changes of Ferrocene-Terminated Self-Assembled Monolayers Induced by Molecularly Thin Ionic Liquid Layers: A Combined Atomic Force Microscopy, X-ray Photoelectron Spectroscopy, and Ultraviolet Photoelectron Spectroscopy Study

Electronic-State Changes of Ferrocene-Terminated Self-Assembled Monolayers Induced by Molecularly Thin Ionic Liquid Layers: A Combined Atomic Force Microscopy, X-ray Photoelectron Spectroscopy, and Ultraviolet Photoelectron Spectroscopy Study

X-ray photoelectron spectroscopy: From origins to future directions

Multiplet splitting in 1s hole states of molecules

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