EPR Interactions – Zero-Field Splittings
2017 - Volume 6 eMagRes
Volume 6, Issue 2
Abstract
Zero-field splitting (ZFS) is a phenomenon that arises in paramagnetic systems with multiple unpaired electrons (i.e., S > 1/2) as a result of both spin–spin coupling (SSC) and spin–orbit coupling (SOC) interactions. ZFS is manifest in EPR spectra of such S > 1 systems by extensive additional (fine structure) transitions. This article begins with the simplest system that exhibits ZFS, namely the spin triplet (S = 1), which is found in organic biradicals, as well as in transition metal (d block) complexes. The energy levels and resulting X-band EPR spectra for triplets where the ZFS is on the order of this microwave quantum (ν ≈ 9 GHz; ν/c ≈ 0.3 cm−1) are presented. The results are easily translated into cases where the ZFS is large, but the applied microwave frequencies and corresponding resonant magnetic fields are large as well, as is found in high-frequency and high-field EPR (HFEPR; ν > 150 GHz; ν/c > 5 cm−1). This article continues case by case, discussing in a similar manner each progressively higher spin system: quartets (S = 3/2), quintets (S = 2), sextets (S = 5/2), septets (S = 3), and octets (S = 7/2), the last of these being applicable to complexes of f7 ions of which Gd(III) is the most important.
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