Chemical bonding properties of liquid methane under high-density conditions

Abstract

We present the chemical bonding and electronic properties of liquid methane at temperatures from 2000 to 4000 K and high densities of up to 3.0 g/cm3, calculated using ab initio molecular dynamics simulations in combination with the Mulliken population analysis. Bond-overlap populations and pair distribution functions are studied to investigate the evolution of electron delocalization accompanying atomic structure change as the density is increased. In addition, we also investigated the bandgap energy, electronic density of states, and spatial distribution of electron density. We observed that molecular hydrogen and C‒C bonds are formed after methane dissociates, and then the system undergoes a nonmetal–metal transition coinciding with hydrogen being transformed from the molecular to the atomic state. The C‒C bonds in the system retain covalent character, even at the highest density of 3.0 g/cm3.