Anharmonicity of inner-OH stretching modes in hydrous phyllosilicates: assessment from first-principles frozen-phonon calculations

Abstract

The theoretical anharmonicity of the inner-OH stretching modes of kaolinite and lizardite is determined using a frozen-phonon approach. The anharmonicity parameter, defined as the difference between half the first overtone frequency and the frequency of the fundamental transition, is −95 and −92 cm−1 for kaolinite and lizardite, respectively. These values are consistent with the experimental measurements. The very good agreement usually observed between harmonic calculations of vibrational frequencies at the density functional theory (DFT) level, using the generalized gradient approximation (GGA), and experimental positions of vibrational bands results from the fortuitous, but almost exact, cancelation of two types of errors. One is related to the GGA approximation and the other to the neglect of anharmonicity.