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Uncovering the Connection Between Low-Frequency Dynamics and Phase Transformation Phenomena in Molecular Solids.

Accepted version
Peer-reviewed

Type

Article

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Authors

Ruggiero, Michael T 
Zhang, Wei 
Bond, Andrew D 
Mittleman, Daniel M 
Zeitler, J Axel 

Abstract

The low-frequency motions of molecules in the condensed phase have been shown to be vital to a large number of physical properties and processes. However, in the case of disordered systems, it is often difficult to elucidate the atomic-level details surrounding these phenomena. In this work, we have performed an extensive experimental and computational study on the molecular solid camphor, which exhibits a rich and complex structure-dynamics relationship, and undergoes an order-disorder transition near ambient conditions. The combination of x-ray diffraction, variable temperature and pressure terahertz time-domain spectroscopy, ab initio molecular dynamics, and periodic density functional theory calculations enables a complete picture of the phase transition to be obtained, inclusive of mechanistic, structural, and thermodynamic phenomena. Additionally, the low-frequency vibrations of a disordered solid are characterized for the first time with atomic-level precision, uncovering a clear link between such motions and the phase transformation. Overall, this combination of methods allows for significant details to be obtained for disordered solids and the associated transformations, providing a framework that can be directly applied for a wide range of similar systems.

Description

Keywords

0306 Physical Chemistry (incl. Structural)

Journal Title

Phys Rev Lett

Conference Name

Journal ISSN

0031-9007
1079-7114

Volume Title

120

Publisher

American Physical Society (APS)
Sponsorship
EPSRC (1198)