On the influence of water on THz vibrational spectral features of molecular crystals.

Sergey Mitryukovskiy,Mélanie Lavancier,Danny E. P. Vanpoucke,Goedele Roos,Djamila Hourlier,Romain Peretti,Yue Bai,Théo Hannotte

doi:10.1039/d1cp03261e

Abstract

The nanoscale structure of molecular assemblies plays a major role in many (μ)-biological mechanisms. Molecular crystals are one of the most simple of these assemblies and are widely used in a variety of applications from pharmaceuticals and agrochemicals, to nutraceuticals and cosmetics. The collective vibrations in such molecular crystals can be probed using terahertz spectroscopy, providing unique characteristic spectral fingerprints. However, the association of the spectral features to the crystal conformation, crystal phase and its environment is a difficult task. We present a combined computational-experimental study on the incorporation of water in lactose molecular crystals, and show how simulations can be used to associate spectral features in the THz region to crystal conformations and phases. Using periodic DFT simulations of lactose molecular crystals, the role of water in the observed lactose THz spectrum is clarified, presenting both direct and indirect contributions. A specific experimental setup is built to allow the controlled heating and corresponding dehydration of the sample, providing the monitoring of the crystal phase transformation dynamics. Besides the observation that lactose phases and phase transformation appear to be more complex than previously thought - including several crystal forms in a single phase and a non-negligible water content in the so-called anhydrous phase - we draw two main conclusions from this study. Firstly, THz modes are spread over more than one molecule and require periodic computation rather than a gas-phase one. Secondly, hydration water does not only play a perturbative role but also participates in the facilitation of the THz vibrations.

Highlights

Water molecules play an essential role in the structural and functional properties of organic compounds
Computational studies (most commonly, Density Functional Theory (DFT) calculations and Molecular Dynamics (MD) simulation) can complement the knowledge gained through experiments and offer a description of the macromolecule or the molecular crystal and solvent as well as their dynamics at the atomic scale[7–11]
Note the signatures of the THz absorption by water vapour becoming visible at 377 K – an indication of water molecules being removed from the lactose crystals, starting at this temperature

Summary

Introduction

Water molecules play an essential role in the structural and functional properties of organic (and even inorganic) compounds. They can be incorporated in organic compounds, hereby creating hydrates through the formation of sub-lattices, organized within the crystal of the host compound. It is not surprising that water in all its forms is probably one of the most widely studied chemical compounds[1]. A wide range of experimental techniques can be used to address the role of water in organic molecular structures: X-ray and neutron diffraction[2], nuclear magnetic resonance (NMR)[3,4] and various optical spectroscopic techniques[5,6]. Computational studies (most commonly, Density Functional Theory (DFT) calculations and Molecular Dynamics (MD) simulation) can complement the knowledge gained through experiments and offer a description of the macromolecule or the molecular crystal and solvent as well as their dynamics at the atomic scale[7–11]

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Methods

Results

Conclusion