  The electronic structure in the new transition metal carbide Ti4SiC3 has been
investigated by bulk-sensitive soft x-ray emission spectroscopy and compared to
the well-studied Ti3SiC2 and TiC systems. The measured high-resolution Ti L, C
K and Si L x-ray emission spectra are discussed with ab initio calculations
based on density-functional theory including core-to-valence dipole matrix
elements. The detailed investigations of the Ti-C and Ti-Si chemical bonds
provide increased understanding of the physical properties of these
nanolaminates. A strongly modified spectral shape is detected for the buried Si
monolayers due to Si 3p hybridization with the Ti 3d orbitals. As a result of
relaxation of the crystal structure and the charge-transfer from Ti (and Si) to
C, the strength of the Ti-C covalent bond is increased. The differences between
the electronic and crystal structures of Ti4SiC3 and Ti3SiC2 are discussed in
relation to the number of Si layers per Ti layer in the two systems and the
corresponding change of materials properties.
