Physical and chemical transformations of highly compressed carbon dioxide at bond energies

Abstract

Carbon dioxide exhibits a richness of high-pressure polymorphs with a great diversity in intermolecular interaction, chemical bonding, and crystal structures. It ranges from typical molecular solids to fully extended covalent solids with crystal structures similar to those of SiO₂. These extended solids of carbon dioxide are fundamentally new materials exhibiting interesting optical nonlinearity, low compressibility and high energy density. Furthermore, the large disparity in chemical bonding between the extended network and molecular structures results in a broad metastability domain for these phases to room temperature and almost to ambient pressure and thereby offers enhanced opportunities for novel materials developments. Broadly speaking, these molecular-to-non-molecular transitions occur due to electron delocalization manifested as a rapid increase in electron kinetic energy at high density. The detailed mechanisms, however, are more complex with phase metastabilities, path-dependent phases and phase boundaries, and large lattice strains and structural distortions – all of which are controlled by well beyond thermodynamic constraints to chemical kinetics associated with the governing phases and transitions. As a result, the equilibrium phase boundary is difficult to locate precisely (experimentally or theoretically) and is often obscured by the presence of metastable phases (ordered or disordered). This paper will review the pressure-induced transformations observed in highly compressed carbon dioxide and present chemistry perspectives on those molecular-to-non-molecular transformations that can be applied to other low-Z molecular solids at Mbar pressures where the compression energy rivals the chemical bond energies.