Simulated Infrared and Raman Spectra of Phosphorus Allotropes

Elemental phosphorus is both an intriguing and challenging case in solid state chemistry. The variety of existing allotropes, with different chemistry and properties, makes this long-time studied element still of high intertest today. In this work, we have systematically investigated the vibrational properties of white (Formula presented.), white (Formula presented.), fibrous red, violet, and black phosphorus allotropes by simulating their infrared (IR) and Raman spectra at the density functional theory (DFT) level. The latter are provided as powder and directionally resolved (oriented single crystal) spectra. As all results are obtained with the same method and computational setup, our work provides a data set that is consistent across the different polimorphs, hence minimizing discrepancies arising from methodological differences. Our results are in general good agreement with available experimental and theoretical spectra from literature in both the Raman and IR cases. At the same time, some of our spectra are meant to fill gaps in the existing literature.