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Volumn 4, Issue 9, 2003, Pages 997-1001

On the covalency of silver-fluorine bonds in compounds of silver(I), silver(II) and silver(III)

Author keywords

Electronic structure; Fluorine; Photoelectron spectroscopy; Silver

Indexed keywords

CHEMICAL BONDS; ELECTRONIC STRUCTURE; FLUORINE; FLUORINE COMPOUNDS; PHOTOELECTRON SPECTROSCOPY; SILVER;

EID: 0141683492     PISSN: 14394235     EISSN: None     Source Type: Journal    
DOI: 10.1002/cphc.200300777     Document Type: Article
Times cited : (84)

References (36)
  • 5
    • 0035800341 scopus 로고    scopus 로고
    • W. Grochala, R. Hoffmann Angew. Chem. 2001, 113, 2816,; Angew. Chem. Int. Ed. 2001, 40, 2743.
    • (2001) Angew. Chem. Int. Ed. , vol.40 , pp. 2743
  • 6
    • 0141497083 scopus 로고    scopus 로고
    • note
    • Thus modified fluorides of Ag(III) and Ag(II) might possibly emerge as a novel family of superconducting materials, analogous in some ways to the well known oxocuprate superconductors. Indeed, sudden drops in the magnetic susceptibility of a large number of samples in the Be-Ag-F system have been observed recently, and attributed to superconductivity at temperatures ranging from 8.5 K to 64 K (W. Grochala, P. P. Edwards, unpublished results).
  • 9
    • 0141608670 scopus 로고    scopus 로고
    • note
    • 2 typically utilized the commercially available, partially decomposed compound.
  • 12
    • 0141497082 scopus 로고    scopus 로고
    • note
    • 2 in the ultrahigh vacuum conditions during the XPS experiment.
  • 14
    • 0141608667 scopus 로고    scopus 로고
    • note
    • 6. Cationic Ag(III) and cationic Ni(IV) are at present the strongest known oxidizers.
  • 16
    • 0141831732 scopus 로고    scopus 로고
    • note
    • DFT computations indicate that the "ligand band" lies below the "metal band" in silver fluorides;[2] for example for AgF the energy difference is some 3 eV, similar to the experimental value of 2.5 eV.
  • 18
    • 0141720385 scopus 로고    scopus 로고
    • note
    • The ionization cross-section of the F(2s) electrons is one order of magnitude smaller than that for the Ag(4d) ones, and the contribution from the former to the valence band is small, according to the calculations[2].
  • 19
    • 0004196699 scopus 로고
    • (Ed. D. Shirley) North Holland, Amsterdam
    • U. Gelius, in Electron Spectroscopy (Ed. D. Shirley) North Holland, Amsterdam, 1972.
    • (1972) Electron Spectroscopy
    • Gelius, U.1
  • 20
    • 0141720383 scopus 로고    scopus 로고
    • note
    • 2 is partially reduced on the surface).
  • 21
    • 0141831731 scopus 로고    scopus 로고
    • note
    • The "ligand band" progressively shifts to lower binding energies in the order AgF > AgCl > AgBr ≈ AgI, and simultaneously gains intensity, thus reflecting the increasing energy of the np orbitals of the nonmetal and their stronger mixing with the Ag(4d) orbitals.
  • 25
    • 0141497076 scopus 로고    scopus 로고
    • note
    • 4), due to the decreasing (shortest) F - F distance in these compounds (3.493 Å, 3.026 Å, 2.843 A, and 2.639 Å, respectively).
  • 26
    • 0141497075 scopus 로고    scopus 로고
    • note
    • The values listed in Table 6 of ref.[4] were normalized so that the sum of contributions is 100 %. Contributions from all silver valence orbitals (4d + 5s + 5p) was in fact taken in ref.[2]. However the contribution from Ag(5s + 5p) states to the valence band is computed to be small and can be neglected in the comparison that follows.
  • 27
    • 0141720379 scopus 로고    scopus 로고
    • note
    • 3, but it should not have significant impact on the quantitative comparison.
  • 28
    • 0141497074 scopus 로고    scopus 로고
    • note
    • 2 is partially reduced, at least on the surface.
  • 29
    • 0141720377 scopus 로고    scopus 로고
    • note
    • Thus it proves not to be only a (computational) artifact of the choice of the Weigner-Seitz radii.
  • 30
    • 0141831728 scopus 로고    scopus 로고
    • note
    • More detailed considerations should involve the difference of the lattice energies of substrate and products.
  • 31
    • 0141608664 scopus 로고    scopus 로고
    • unpublished results
    • 3 studied here, proves to be metallic: W. Grochala, P. P. Edwards, unpublished results.
    • Grochala, W.1    Edwards, P.P.2
  • 32
    • 0141720378 scopus 로고    scopus 로고
    • http://www.dl.ac.uk/RUSTI/xps/esca300.htm
  • 33
    • 0003828439 scopus 로고
    • (Ed. D. Briggs, M. P. 5eah), Wiley, Chichester
    • Practical Surface Analysis (Ed. D. Briggs, M. P. 5eah), Wiley, Chichester 1990.
    • (1990) Practical Surface Analysis


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.