Sl. Stoll et al., COPPER K-EDGE X-RAY-ABSORPTION STUDIES OF LA2-XKXCUO4 SUPERCONDUCTORS, BA4NACUO4(CO3)(2), AND NDCU2O4, Inorganic chemistry, 36(9), 1997, pp. 1838-1841
X-ray near-edge absorption spectroscopy (XANES) measurements are repor
ted at the Cu K-edge for La2-xKxCuO4 superconductors with x = 0.1 and
0.2. Comparisons of the data were made with the absorption spectra of
a Cu(II) standard (La2CuO4), a new Cu(III) standard (Ba4NaCuO4(CO3)(2)
), and a new mixed-valent Cu(II)/Cu(III) phase (NdCu2O4). There is a c
onsistent increase in the energy of the main Cu absorption edge in the
following series: La2CuO4 < La1.9K0.1CuO4 < La1.8K0.2CuO4 similar to
NdCu2O4 < Ba4NaCuO4(CO3)(2). This trend can be attributed to an increa
se in the average Cu valence and to a decrease in bond length and an i
ncrease in covalency. The magnitude of the energy shift from Cu(II) to
Cu(III) for the main absorption edge is similar to 3 eV. There is no
measurable change in the energy of the pre-edge feature irrespective o
f Cu valence. Furthermore, no new features appear at the edge for samp
les with formal oxidation state between 2 and 3, even for NdCu2O4, whi
ch contains both Cu(II) and Cu(III) in crystallographically distinct s
ites.