Systematic Absences of Optical Phonon Modes in Phonon Dispersion Measured by Electron Microscopy

Phonon dispersion relations are widely used to elucidate the vibrational properties of materials. As an emerging technique, momentum-resolved vibrational spectroscopy in scanning transmission electron microscopy offers an unparalleled approach to explore q-dependent phonon behavior at local structures. In this study, we systematically investigate the phonon dispersion of monolayer graphene across several Brillouin zones (BZs) using momentum-resolved vibrational spectroscopy and find that the optical phonon signals vanish at the Γ points with indices (hk0) satisfying h+2k=3n (n denoted integers). Theoretical analysis reveals that the observed phenomena arise from the complete destructive interference of the scattered waves from different basis atoms. This observation, corroborated by the study of diamond, should be a general characteristic of materials composed of symmetrically equivalent pairs of the same elements. Moreover, our results emphasize the importance of multiple scattering in interpreting the vibrational signals in bulk materials. We demonstrate that the systematic absences and dynamic effects, which have not been much appreciated before, offer new insights into the experimental assessment of local vibrational properties of materials.