High energy photoelectron spectroscopy of transition metal complexes. Part 3.—Direct measurement and interpretation of the core level shifts between free and complexed CO, and the bonding in some substituted manganese pentacarbonyls

Connor, Joseph A.; Hall, Michael B.; Hillier, Ian H.; Meredith, W.N.E.; Barber, M.; Herd, Q. C.

doi:10.1039/f29736901677

Cited by 39 publications

(7 citation statements)

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“…The measured carbon intramolecular splitting is seriously overestimated by the theoretical i.p. 's in line with a similar result for Mn(CO)sCH 3 [20]. This may be due to an inadequacy in the basis used in the present calculations or to a greater orbital relaxation being associated with core ionization from the carbonyl carbon atoms than from the carbon atoms of the hydrocarbon, as previously suggested [21].…”

Section: High Energy Photoelectron Spectra Of Iron Tricarbonyl Butadienesupporting

confidence: 89%

“…This may be due to an inadequacy in the basis used in the present calculations or to a greater orbital relaxation being associated with core ionization from the carbonyl carbon atoms than from the carbon atoms of the hydrocarbon, as previously suggested [21]. As in other carbonyl complexes [20,21], a satellite peak to high binding energy of the main carbon ls peak is observed. In view of the intensity ratio of the two main peaks being less, rather than greater than 1.33 : 1, we cannot associate this satellite solely with the CO carbon ionizations.…”

Section: High Energy Photoelectron Spectra Of Iron Tricarbonyl Butadienementioning

confidence: 65%

“…t These differ slightly from those previously published[20], as we here use the CO i.p. 's of[10] for calibration purposes.…”

mentioning

confidence: 63%

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The electronic structure of transition metal complexes containing organic ligands

et al. 1974

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The He(I), He(II) and X-ray photoelectron spectra of iron tricarbonyl butadiene are reported and these measurements, together with the bonding in the complex, are discussed with the aid of ab initio SCF MO calculations. The latter yield a substantial negative charge on the butadiene ligand, and the low energy photoelectron spectra can only be satisfactorily interpreted when deviations from Koopmans' theorem are taken into account by performing RHF calculations on the various low-lying ionic states of the molecule. M.P. 4 I

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Section: High Energy Photoelectron Spectra Of Iron Tricarbonyl Butadienesupporting

confidence: 89%

Section: High Energy Photoelectron Spectra Of Iron Tricarbonyl Butadienementioning

confidence: 65%

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The electronic structure of transition metal complexes containing organic ligands

et al. 1974

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“…The same conclusion was suggested by the failure of Koopmans' theorem calculations in reproducing the observed IE shifts. 32 In a previous ETS and MSstudy of (benzene)chromium tricarbonyl, (cyclopentadieny 1)manganese tricarbonyl, (butadiene) iron tricarbonyl, and (cyclopentadienyl)cobalt tricarbonyl3 we found charge distributions analogous to those obtained here for the carbonyl complexes, that is, a largely negative metal center.…”

Section: Charge Distributionssupporting

confidence: 78%

Characterization of the temporary anion states of metal carbonyl complexes: an MS-X.alpha. and ETS study of chromium hexacarbonyl and iron pentacarbonyl

Guerra¹,

Jones²,

Distefano³

et al. 1988

J. Am. Chem. Soc.

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“…The peak at ~399.1-399.3 eV on both treated slides is from N of acetonitrile used in the final wash step. 115 The peak at ~401.2 eV has been attributed to the nitrogen bounded to oxygen. 116,117 However, it does not explain the absence of this peak on the formamide treated surfaces.…”

Section: ) Chemical Identification Of Treated Pyrite Surfacementioning

confidence: 99%

The Influence of Surface Chemistry on the Photoelectrochemical Properties of FeS(2) Photoanodes

Qi¹

2000

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The recurring theme of this dissertation is the correlation between FeS 2 surface chemistry and key electrical and electronic properties of FeS 2. Efforts have been made to identify and characterize the FeS 2 surface, investigate the photoelectrochemistry of FeS 2 photoanodes under anhydrous and anoxic conditions, and investigate the influence of deliberate surface chemistry on FeS 2 photoelectrochemistry. Infrared reflection-absorption spectroscopy (IRRAS) was used to investigate a thin adsorbate layer on pyrite. The results showed that the combination of angledependent studies and computational efforts are a powerful tool for characterizing the pyrite surface. The photoelectrochemistry of FeS 2 photoanodes was investigated in an I-/I 3 acetonitrile electrolyte. The results revealed that the non-aqueous system was suitable for strictly anhydrous and anoxic photoelectrochemical studies. A model was proposed to explain the observed influence of concentration of dissolved I 2 on the photovoltage. A central component of the proposed model was that shunting was assumed to take place at physically distinct regions of the electrode and that mass-transport to and from these regions could be treated separately from mass-transport to the regions responsible for the rectifying behavior of the FeS 2 /liquid junction. The implication of the agreement between experimental and calculated J-E curves is that macroscopic photoelectrochemical investigations may underestimate the quality of FeS 2 photoanodes due to the presence of defects. ii The influence of surface treatments on FeS 2 photoelectrochemistry was further studied using non-coordinating redox species. A statistically significant increase of photovoltage was observed after treating FeS 2 surfaces with KCN. X-ray photoelectron spectroscopy was used to study chemical bond formation between the electron donating ligands and iron(II) centers on the pyrite surface. The results were discussed in terms of charge recombination models and surface coordination chemistry. Unfinished work is also presented. Cathodic polarization in acidic media is a prerequisite for any detectable photoresponse. The exact function of the electrochemical activations was further investigated by electropolishing pyrite electrode under different experimental conditions including etchant identity and applied bias. The results suggested that the electrochemical treatment removes the damaged surface layer caused by mechanical polishing, and might also stabilize the surface states. Further experiments can be focus on anhydrous etching of pyrite photoanode. The research presented in this dissertation guides future studies of thin film FeS 2 photovoltaics. iii Dedication This dissertation is dedicated to my family. iv Acknowledgments I wish to express my sincere gratitude to my advisor Prof. Erik Johansson. His broad knowledge and logical way of thinking have been of great value for me. The present dissertation would not have been possible without his encouragement and supervision. I would like to thank Pro...

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High energy photoelectron spectroscopy of transition metal complexes. Part 3.—Direct measurement and interpretation of the core level shifts between free and complexed CO, and the bonding in some substituted manganese pentacarbonyls

Cited by 39 publications

References 0 publications

The electronic structure of transition metal complexes containing organic ligands

The electronic structure of transition metal complexes containing organic ligands

Characterization of the temporary anion states of metal carbonyl complexes: an MS-X.alpha. and ETS study of chromium hexacarbonyl and iron pentacarbonyl

The Influence of Surface Chemistry on the Photoelectrochemical Properties of FeS(2) Photoanodes

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