We report a study of high-resolution microwave spectroscopy of nitrogen-vacancy centers in diamond crystals at and around zero magnetic field. We observe characteristic splitting and transition imbalance of the hyperfine transitions, which originate from level anti-crossings in the presence of a transverse effective field. For clearly resolving such level anti-crossings, we use pulsed electron spin resonance spectroscopy to measure the zero-field spectral features of single nitrogen-vacancy centers. To quantitatively analyze the magnetic resonance behavior of the hyperfine spin transitions in the presence of the effective field, we present a theoretical model, which describes the transition strengths under the action of an arbitrarily polarized microwave magnetic field. Our results are of importance for the optimization of the experimental conditions for the polarization-selective microwave excitation of spin-1 systems in zero or weak magnetic fields.

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