Hydrogen detection is essential for its implementation as an energy vector. So far, palladium is considered to be the most effective hydrogen sensing material. Here we show that palladium-capped hafnium thin films show a highly reproducible change in optical transmission in response to a hydrogen exposure ranging over six orders of magnitude in pressure. The optical signal is hysteresis-free within this range, which includes a transition between two structural phases. A temperature change results in a uniform shift of the optical signal. This, to our knowledge unique, feature facilitates the sensor calibration and suggests a constant hydrogenation enthalpy. In addition, it suggests an anomalously steep increase of the entropy with the hydrogen/metal ratio that cannot be explained on the basis of a classical solid solution model. The optical behaviour as a function of its hydrogen content makes hafnium well-suited for use as a hydrogen detection material.

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We calculate from first principles the optical spectra of the hydrides in the sodium alanate hydrogen storage system: NaH, NaAlH4, and Na 3AlH6. In particular we study the effects of systematic improvements of the theoretical description. To benchmark the calculations we also measure the optical response of a thin film of NaH. The simplest calculated dielectric functions are based upon independent electrons and holes, whose spectrum is obtained at the G0W0 level. Successive improvements consist of including partial self-consistency (so-called GW 0) and account for excitonic effects, using the Bethe-Salpeter equation (BSE). Each improvement gives a sizable blue shift or red shift of the dielectric functions, but conserves the trend in the optical gap among different materials. Whereas these shifts partially cancel at the highest (GW 0-BSE) level of approximation, the shape of the dielectric functions is strongly modified by excitonic effects. Calculations at the GW 0-BSE level give a good agreement with the dielectric function of NaH extracted from the measurements. It demonstrates that the approach can be used for a quantitative interpretation of spectra in novel hydrogen storage materials obtained via, e.g., hydrogenography.@en