Local Proton Disorder Induced Intermolecular H-H Coupling in Ionization of Dense Ammonia

Abstract

Under cold compression, hydrogen bonding was considered to dominate intermolecular interaction during the ionization of ammonia. Here, we provide experimental and theoretical evidence of intermolecular HH coupling in dense ammonia. Ab initio molecular dynamics simulations (AIMD) reveal an increasing degree of proton disorder in ammonia with increasing pressure, which promotes intermolecular H-H coupling. At pressure below the ionization phase transition pressure (135 GPa), intermolecular HH coupling gives rise to a unique dissociation pathway in ammonia. Sporadic molecular hydrogen was observed without laser heating, accompanied by the absence of molecular nitrogen. At pressure above 135 GPa, intermolecular HH coupling serves as an intermediate state in the ionization of ammonia. Two fingerprint Raman modes previously assigned to the ionic phase disappear upon further compression or heating. Together with proton transfer based on hydrogen bond, a dual path mechanism exists in the ionization of ammonia. Our results demonstrate a case of hydrides phase transition pathway that occurs independently of hydrogen bonding under high pressure.