Novel Porous Polymorphs of Zinc Cyanide with Rich Thermal and Mechanical Behavior

TL;DR

This study uses computational methods to explore new porous zinc cyanide polymorphs, revealing their thermal and mechanical behaviors, including negative thermal expansion and pressure-induced softening, expanding understanding of this material family.

Contribution

It predicts seven novel porous Zn(CN)2 phases and characterizes their thermal and mechanical properties using quantum chemical and molecular dynamics simulations.

Findings

Confirmed metastability of two known porous phases.

Predicted seven new porous phases of Zn(CN)2.

All structures exhibit negative thermal expansion.

Abstract

We investigate the feasibility of four-connected nets as hypothetical zinc cyanide polymorphs, as well as their thermal and mechanical properties, through quantum chemical calculations and molecular dynamics simulations. We confirm the metastability of the two porous phases recently discovered experimentally (Lapidus, S. H.; et al. J. Am. Chem. Soc. 2013, 135, 7621-7628), suggest the existence of seven novel porous phases of Zn(CN)2, and show that isotropic negative thermal expansion is a common occurrence among all members of this family of materials, with thermal expansion coefficients close to that of the dense dia-c phase. In constrast, we find a wide variety in the mechanical behavior of these porous structures with framework-dependent anisotropic compressibilities. All porous structures, however, show pressure-induced softening leading to a structural transition at modest pressure.