Insight into the structure of black coatings of ancient Egyptian mummies by advanced Electron magnetic resonance of vanadyl complexes

Advanced EPR techniques such as ENDOR and pulsed EPR are used to investigate the enigmatic black coatings of ancient Egyptian mummies, consisting in a complex and heterogeneous mixtures of conifer resins, wax, fat and oil with variable amounts of bitumen. Natural bitumen always contains traces of vanadyl porphyrin complexes that we used here as internal probes to explore the nanoscale environment of V4+ ions in these black coatings by hyperfine spectroscopy. Four types of vanadyl porphyrins were identified from the analysis of 14N hyperfine interactions. Three types (referred to as VO-P1, VO-P2 and VO-P3) are present in natural bitumen from the Dead Sea, among which VO-P1 and VO-P2 are also present in black coatings of mummies. The absence of VO-P3 in mummies, which is replaced by another complex VO-P4, may be due to its transformation during preparation of the black matter for embalming. Analysis of 1H hyperfine interaction shows that bitumen and other natural substances are intimately mixed in these black coatings, with bitumen aggregate sizes not larger than a few nanometres.

Hyperfine spectroscopy in a quantum-limited spectrometer

We report measurements of electron-spin-echo envelope modulation (ESEEM) performed at millikelvin temperatures in a custom-built high-sensitivity spectrometer based on superconducting micro-resonators. The high quality factor and small mode volume (down to 0.2 pL) of the resonator allow us to probe a small number of spins, down to 5×102. We measure two-pulse ESEEM on two systems: erbium ions coupled to 183W nuclei in a natural-abundance CaWO4 crystal and bismuth donors coupled to residual 29Si nuclei in a silicon substrate that was isotopically enriched in the 28Si isotope. We also measure three- and five-pulse ESEEM for the bismuth donors in silicon. Quantitative agreement is obtained for both the hyperfine coupling strength of proximal nuclei and the nuclear-spin concentration.

Hyperfine spectroscopy in a quantum-limited spectrometer

We report measurements of electron spin echo envelope modulation (ESEEM) performed at millikelvin temperatures in a custom-built high-sensitivity spectrometer based on superconducting micro-resonators. The high quality factor and small mode volume (down to 0.2 pL) of the resonator allow to probe a small number of spins, down to 5 ⋅ 102. We measure 2-pulse ESEEM on two systems: erbium ions coupled to 183W nuclei in a natural-abundance CaWO4 crystal, and bismuth donors coupled to residual 29Si nuclei in a silicon substrate that was isotopically enriched in the 28Si isotope. We also measure 3- and 5-pulse ESEEM for the bismuth donors in silicon. Quantitative agreement is obtained for both the hyperfine coupling strength of proximal nuclei, and the nuclear spin concentration.