Abstract
This work demonstrates the usefulness of pulsed electron spin resonance (ESR)-based two-dimensional electron spin transient nutation (2-D ESN) spectroscopy for complete assignments of complicated fine-structure hyperfine ESR spectra including hyperfine forbidden transitions from electronic and nuclear high-spin systems. The 2-D ESN spectroscopy is termed transition moment spectroscopy as spectra are acquired as a function of transition moment instead of transition energy used in conventional spectroscopy. We have applied the novel spectroscopic technique to Eu2+ ion (S=7/2,I=5/2), which has two isotopes (151Eu [47.9%] and153Eu [52.1%]), in a CaF2 single crystal as a model system. We have completely identified the complicated fine-structure hyperfine ESR spectra by invoking the spectral simulation of the 2-D ESN spectra on the basis of transition moment analyses. The analyses are based on exact numerical calculations of the transition moments as well as a perturbation-based analytical approach combined with reduced rotation matrices for the nuclear part of the transition moment. This is the first example of the spectral simulation for 2-D ESN spectra including the hyperfine allowed and forbidden transitions in high-spin systems. In addition, we have made simulation of the fine-structure forbidden transitions, which reproduces the angular variations of the observed spectra at liquid helium temperatures.
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Matsuoka, H., Sato, K., Shiomi, D. et al. 2-D electron spin transient nutation spectroscopy of Lanthanoid ion Eu2+(8S7/2) in a CaF2 single crystal on the basis of FT-pulsed electron spin resonance spectroscopy: Transition moment spectroscopy. Appl. Magn. Reson. 23, 517–538 (2003). https://doi.org/10.1007/BF03166639
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DOI: https://doi.org/10.1007/BF03166639