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Abstract

The characterization of zeolitic materials is often facilitated by spectroscopic analysis of vibrations, which informs about the bonding character of the substrate and any adsorbents. Computational simulations aid the interpretation of the spectra but often ignore anharmonic effects that can affect the spectral characteristics significantly. Here, the impact of anharmonicity is demonstrated with a combination of dynamical and static simulations applied to the structures formed during the synthesis of Sn-BEA via solid-state incorporation (SSI): the initial siliceous BEA (Si-β), aluminosilicate BEA (H-β), dealuminated BEA (deAl-β), and Sn-BEA (Sn-β). Heteroatom and defect-containing BEA are shown to have strong anharmonic vibrational contributions, with atomic and elemental resolution highlighting particularly the prevalence for H atoms (H-β, deAl-β) as well as localization to heteroatoms at defect sites. We simulate the vibrational spectra of BEA accounting for anharmonic contributions and observe an improved agreement with experimental data compared to harmonic methods, particularly at wavenumbers below 1500 cm^–1. The results demonstrate the importance of incorporating anharmonic effects in simulations of vibrational spectra, with consequences toward future characterization and application of zeolitic materials.