Polymorphism of resorcinol explored by complementary vibrational spectroscopy (FT-RS, THz-TDS, INS) and...

Area of Science:

• Solid-state chemistry
• Materials science
• Computational physics

Background:

• Polymorphism in resorcinol is crucial for understanding its solid-state behavior.
• Temperature-induced phase transitions significantly alter resorcinol's structural and spectral properties.

Purpose of the Study:

• To comprehensively investigate resorcinol polymorphism using combined experimental and computational methods.
• To interpret spectral differences arising from phase transitions, focusing on low-wavenumber vibrational modes.
• To evaluate the performance of different density functional theory (DFT) functionals for predicting resorcinol's structural and vibrational properties.

Main Methods:

• Raman spectroscopy
• Time-domain terahertz spectroscopy
• Inelastic neutron scattering spectroscopy
• Plane-wave density functional theory (DFT) calculations
• Generalized gradient approximation (GGA) functionals (PBE, PBE-hard, PBE-soft)

Main Results:

• Experimental spectra were successfully reproduced by DFT calculations, particularly in the low-wavenumber range.
• The source of spectral differences observed during temperature-induced phase transitions was identified.
• The Perdew, Burke, and Ernzerhof (PBE) functional, especially its "hard" revised form, demonstrated superior performance in predicting structural parameters and vibrational spectra compared to other GGA functionals.

Conclusions:

• Combined spectroscopic and DFT approaches effectively elucidate resorcinol polymorphism.
• DFT calculations, particularly with the PBE functional, are reliable for studying solid-state phase transitions and vibrational properties.
• Understanding resorcinol's polymorphic behavior is enhanced by accurate computational modeling.