Classification of a material either as a semiconductor or a semimetal can become tricky when it has extremely small or slightly negative band-gaps. The well-known compound Fe 2 VAl for example, was historically thought of as a semi-metal (with a negative gap ~ -0.1 eV) for over two decades before it was actually shown to be a small-gap (~ 0.03 eV) semiconductor using self-consistent analysis of the transport properties, electrical resistivity and Seebeck coefficient. Commonly used experimental techniques to investigate band-gap can be sensitive to many things such as the size of the band-gap, electronic structure features (direct versus indirect gap) and also the number of free charge carriers (which can frequently depend on synthesis conditions). Band-gap obtained from transport property modeling is essentially independent of such factors. Theoretical techniques to calculate the electronic structure on the other hand can often underestimate band-gap.