Negative Linear Compressibility of Formate Crystals from the Viewpoint of Quantum Electronic Pressure

Abstract

In order to understand the phenomenon of negative linear compressibility (NLC) in organic crystals, it is necessary to investigate not only the structural features but also the electronic changes taking place under external hydrostatic pressure. It is also necessary to clarify which electronic properties allow the quantification and comparison of the compressibility of crystals. In our study, the crystal structures of sodium and cadmium formates under hydrostatic compression were modeled, as well as the α and β-phases of calcium formate. The changes in cell parameters and spatial dependences of the linear compressibility were analyzed, and the ranges of external pressure, which must be applied for NLC onset, were predicted for the sodium and α-calcium formates. Although the behavior of chemical bonds is not predicted by the sign or absolute value of the quantum electronic pressure, its relative change under external pressure clearly distinguishes the soft and rigid regions in a crystal. The relationship between the NLC values and the changes in quantum electronic pressure in the cavities of formate crystals was established.

Keywords

• negative linear compressibility
• quantum electronic pressure
• DFT
• formate
• noncovalent bonds
• hydrostatic pressure