ABSTRACT
We study the unoccupied electronic structure of the spin-1/2 quantum magnet TiOCl using x-ray absorption near-edge spectroscopy (XANES) at the Ti L and O K edges. We acquire data both in total electron and fluorescence yield modes (TEY and FY, respectively). While only the latter allows us to access the unconventional low-temperature spin-Peierls (SP) phase of TiOCl, the signal is found to suffer from significant self-absorption in this case. Nevertheless, we conclude from FY data that effects of the SP distortion on the electronic structure are absent in the incommensurate intermediate phase within experimental accuracy. The similarity of room-temperature FY and TEY data, the latter not being obscured by self-absorption, allows us to use TEY spectra for comparison with simulations. These are performed by means of cluster calculations in D(4h) and D(2h) symmetries using two different codes. We extract values of the crystal-field splitting and parameterize our results using the commonly seen notation of Slater, Racah and Butler. In all cases, good agreement with published values from other studies is found.
ABSTRACT
The production and spectroscopic characterization of fullerene-encapsulated metal-atom clusters is reported. In particular, both solution and solid-state electron paramagnetic resonance (EPR) spectra of Sc(3)C(82) have been obtained. ScC(82) also gives an EPR spectrum, but Sc2Cn species-the most abundant metallofullerenes in the mass spectrum-are EPR-silent even though Sc(2) is EPR-active in a rare-gas matrix at 4.2 K. The results suggest that the three scandium atoms in Sc(3)C(82) form an equilateral triangle-as was previously suggested for Sc(3) molecules isolated in a cryogenic rare-gas matrix. The spectrum of ScC(82) has features similar to those found earlier for LaC(82) and YC(82), suggesting that it can also be described as a +3 metal cation within a -3 fullerene radical anion. An implication of this work is that production of macroscopic quantities of clustercontaining fullerenes may make possible the fabrication of exotic new structures with regular arrays of metal-atom clusters isolated in fullerene molecules, resulting in a new type of host/guest nanostructured material.
