Pressure-induced stabilization of carbonic acid and other compounds in the C-H-O system

TL;DR

This study uses computational methods to predict new high-pressure compounds in the C-H-O system, including stabilized carbonic acid and related molecules, revealing pressure-driven chemical transformations relevant to planetary science.

Contribution

The paper introduces a comprehensive crystal structure prediction of the C-H-O system up to 400 GPa, discovering new stable compounds and high-pressure chemistry phenomena.

Findings

Carbonic acid forms at ~1 GPa, stable at higher pressures.

New stable polymorphs of elements and molecules identified.

High-pressure reactions produce orthocarbonic acid above 300 GPa.

Abstract

The physicochemical behavior of elements and compounds is heavily altered by high pressure. The occurrence of pressure-induced reactions and phase transitions can be revealed by crystal structure prediction approaches. In this work, we explore the C-H-O phase diagram up to 400 GPa exploiting an evolutionary algorithm for crystal structure predictions along with ab initio calculations. Besides uncovering new stable polymorphs of high-pressure elements and known molecules, we predicted the formation of new compounds. A 2CH4:3H2 inclusion compound forms at low pressure and remains stable up to 215 GPa. Carbonic acid (H2CO3), highly unstable at ambient conditions, was predicted to form exothermically at mild pressure (about 1 GPa). As pressure rises, it polymerizes and, above 300 GPa, reacts with water to form orthocarbonic acid (H4CO4). This unexpected high-pressure chemistry is rationalized by analyzing charge density and electron localization function distributions, and implications for general chemistry and planetary science are also discussed.