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We present an electron spectroscopy study of phase-pure AC(60) thin films (A = Rb, Cs) in their monomer (face-centred cubic (fcc)) and polymer phases. A surface electronic reconstruction is observed in polymeric RbC60, analogous to that reported for the fcc phase. As for pristine C-60, the occupied electronic states of AC(60) fullerides are not dramatically affected by polymerization. The energy separation between the leading feature in photoemission and inverse photoemission is similar in both stable AC(60) phases. These observations suggest that electron correlation effects are similar in the two phases, and that their different electronic behaviour is mainly related to the reduction of degeneracy of the polymer frontier states. Photoemission and electron-energy loss spectroscopy data show that the thin-film form of the RbC60 polymer is metallic at room temperature, and that it undergoes a metal-insulator transition at around 100 K. This transition temperature is much higher than that reported for the corresponding bulk phase and signals a poorer screening of Coulomb interactions at the film surface.

NaxC60 thin films with Na concentration 0 ⩽ x ⩽ 3 were investigated using angle-dependent photoelectron spectroscopy. For low doping we observed two distinct fulleride phases coexisting with regions of pristine C60. One of these fulleride phase is predominantly formed close to the surface and disappears after annealing and further addition of Na. At higher doping a phase with stoichiometry of x = 3 is formed.

A crystalline sample of TiOBr is probed at room temperature by a combination of electron spectroscopies and the results are compared to theoretical embedded-cluster calculations. Resonant photoemission of the valence band confirms that the lowest binding energy feature arises from the singly occupied Ti 3d orbital. The polarization dependence of this orbital in nonresonant photoemission is consistent with the expected dominant d(y)(2)-z(2) character. The analysis of the Ti L(2,3) x-ray absorption spectra confirms the complete splitting of the Ti 3d shell. X-ray absorption and resonant photoemission at the O 1s edge provide direct evidence for hybridization between the transition metal orbitals and the O 2p levels, which leads to superexchange interactions between the Ti ions. The existence of a mixing of O and Ti states and of strong superexchange interactions is supported by calculations of the ground-state electronic and magnetic properties. The calculated superexchange interchain interaction is one fifth in strength of the total magnetic coupling along the chain, and is antiferromagnetic in character. This O-mediated interchain interaction is frustrated in the room temperature phase of TiOBr and thus couples strongly to distortions of the soft lattice. The competition between the interchain magnetoelastic coupling and the spin-Peierls interaction might be at the origin of the complex TiOX phase diagram.