Design and construction of a broadband electron‐nuclear double resonance (ENDOR) spectrometer with polarization‐modulated radio frequency fields (PM‐ENDOR) is reported. With this type of field configuration, each ENDOR resonance line is labeled by additional parameters so that the interpretation of complicated single‐crystal ENDOR spectra may be considerably simplified. Details of the electronics and the X‐band microwave cavity suitable to generate polarization‐modulated rf fields in the frequency range 2–50 MHz are described. The quality of the PM field over the sample volume is investigated. Performance of the spectrometer is exemplified by applications on transition metal complexes.

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