Vibrational Properties of CuO and Cu 4 O 3 from First-Principles Calculations, and Raman and Infrared Spectroscopy

A combined experimental and theoretical study is reported on the vibrational properties of tenorite CuO and paramelaconite Cu 4 O 3 . The optically active modes have been measured by Raman scattering and infrared absorption spectroscopy. First-principles calculations have been carried out with the LDA+U approach to account for strong electron correlation in the copper oxides. The vibrational properties have been computed ab initio using the so-called direct method. Excellent agreement is found between the measured Raman and infrared peak positions and the calculated phonon frequencies at the Brillouin zone center, which allows the assignment of all prominent peaks of the Cu 4 O 3 spectra. Through a detailed analysis of the displacement eigenvectors, it is shown that a close relationship exists between the Raman modes of CuO and Cu 4 O 3 .