Polymorphism of Resorcinol Explored by Complementary Vibrational Spectroscopy (FT-RS, THz-TDS, INS) and First-Principles Solid-State Computations (Plane-Wave DFT)

• Published in: The journal of physical chemistry. B 2015-01, Vol.119 (4), p.1681-1695
• Main Authors: Drużbicki, Kacper, Mikuli, Edward, Pałka, Norbert, Zalewski, Sławomir, Ossowska-Chruściel, Mirosława D
• Format: Article
• Language: English
• Subjects: Approximation; Computation; Mathematical analysis; Models, Chemical; Models, Molecular; Neutron scattering; Polymorphism; Quantum Theory; Resorcinols - chemistry; Resorcinols - classification; Spectra; Spectroscopy; Spectrum Analysis, Raman; Vibration; Vibrational spectra
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp507241j

The polymorphism of resorcinol has been complementary studied by combining Raman, time-domain terahertz, and inelastic neutron scattering spectroscopy with modern solid-state density functional theory (DFT) calculations. The spectral differences, emerging from the temperature-induced structural phase transition, have been successfully interpreted with an emphasis on the low-wavenumber range. The given interpretation is based on the plane-wave DFT computations, providing an excellent overall reproduction of both wavenumbers and intensities and revealing the source of the observed spectral differences. The performance of the generalized gradient approximation (GGA) functionals in prediction of the structural parameters and the vibrational spectra of the normal-pressure polymorphs of resorcinol has been extensively examined. The results show that the standard Perdew, Burke, and Ernzerhof (PBE) approach along with its “hard” revised form tends to be superior if compared to the “soft” GGA approximation.