Water is a superacid at extreme thermodynamic conditions

Abstract

The chemical behavior of water under extreme pressures and temperatures lies at the heart of processes shaping planetary interiors, influences the deep carbon cycle, and underpins innovative high-temperature, high-pressure synthesis of materials. Recent experiments reveal that hydrocarbons immersed in ionized water under extreme conditions transform into heavy hydrocarbons and nanodiamonds. However, the chemistry of water at extreme conditions and its role in hydrocarbon condensation remains poorly understood. Here, using ab initio molecular dynamics simulations with enhanced sampling techniques and machine-learning interatomic potentials, we show that increasing pressure at high temperature induces water ionization, creating a superacid-like environment that favors the protonation of hydrocarbons into transient pentacoordinated carbonium ions like CH$_5^+$. These elusive intermediates release molecular hydrogen and yield highly reactive carbocations, driving hydrocarbon chain growth toward nanodiamonds. We demonstrate how the combination of water ionization and pressure-induced methane polarization leads to superacid-driven hydrocarbon chemistry, famously known at far milder conditions. Our findings reveal, for the first time, a superacid aqueous regime and establish the existence of superacid chemistry under extreme conditions. Moreover, they provide a unifying reaction network that explains chemical transformations in environments such as planetary interiors and high pressure, high temperature experiments.