Stability of Proton Superoxide and its Superionic Transition Under High Pressure

Abstract Under extreme conditions, condensed matters are subject to undergo a phase transition and there have been many attempts to find another form of hydroxide stabilized over H2O. Here, using Density Functional Theory (DFT)‐based crystal structure prediction including zero‐point energy, it is th...

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Main Authors: Zifan Wang, Wenge Yang, Duck Young Kim
Format: Article
Language:English
Published: Wiley 2025-03-01
Series:Advanced Science
Subjects:
Online Access:https://doi.org/10.1002/advs.202415387
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author Zifan Wang
Wenge Yang
Duck Young Kim
author_facet Zifan Wang
Wenge Yang
Duck Young Kim
author_sort Zifan Wang
collection DOAJ
description Abstract Under extreme conditions, condensed matters are subject to undergo a phase transition and there have been many attempts to find another form of hydroxide stabilized over H2O. Here, using Density Functional Theory (DFT)‐based crystal structure prediction including zero‐point energy, it is that proton superoxide (HO2), the lightest superoxide, can be stabilized energetically at high pressure and temperature conditions. HO2 is metallic at high pressure, which originates from the 𝜋* orbitals overlap between adjacent superoxide anions (O2−). By lowering pressure, it undergoes a metal‐to‐insulator transition similar to LiO2. Ab initio molecular dynamics (AIMD) calculations reveal that HO2 becomes superionic with high electrical conductivity. The possibility of creating hydrogen‐mixed superoxide at lower pressure using a (Lix,H1‐x)O2 hypothetical structure is also proposed. This discovery bridges gaps in superoxide and superionicity, guiding the design of various H‐O compounds under high pressure.
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publishDate 2025-03-01
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spelling doaj-art-f64fa43575a14a32b8fcdc569293ea3a2025-08-20T02:35:35ZengWileyAdvanced Science2198-38442025-03-01129n/an/a10.1002/advs.202415387Stability of Proton Superoxide and its Superionic Transition Under High PressureZifan Wang0Wenge Yang1Duck Young Kim2Center for High Pressure Science & Technology Advanced Research (HPSTAR) Shanghai 201203 P.R. ChinaCenter for High Pressure Science & Technology Advanced Research (HPSTAR) Shanghai 201203 P.R. ChinaCenter for High Pressure Science & Technology Advanced Research (HPSTAR) Shanghai 201203 P.R. ChinaAbstract Under extreme conditions, condensed matters are subject to undergo a phase transition and there have been many attempts to find another form of hydroxide stabilized over H2O. Here, using Density Functional Theory (DFT)‐based crystal structure prediction including zero‐point energy, it is that proton superoxide (HO2), the lightest superoxide, can be stabilized energetically at high pressure and temperature conditions. HO2 is metallic at high pressure, which originates from the 𝜋* orbitals overlap between adjacent superoxide anions (O2−). By lowering pressure, it undergoes a metal‐to‐insulator transition similar to LiO2. Ab initio molecular dynamics (AIMD) calculations reveal that HO2 becomes superionic with high electrical conductivity. The possibility of creating hydrogen‐mixed superoxide at lower pressure using a (Lix,H1‐x)O2 hypothetical structure is also proposed. This discovery bridges gaps in superoxide and superionicity, guiding the design of various H‐O compounds under high pressure.https://doi.org/10.1002/advs.202415387high pressurephase transitionsuperionicitysuperoxides
spellingShingle Zifan Wang
Wenge Yang
Duck Young Kim
Stability of Proton Superoxide and its Superionic Transition Under High Pressure
Advanced Science
high pressure
phase transition
superionicity
superoxides
title Stability of Proton Superoxide and its Superionic Transition Under High Pressure
title_full Stability of Proton Superoxide and its Superionic Transition Under High Pressure
title_fullStr Stability of Proton Superoxide and its Superionic Transition Under High Pressure
title_full_unstemmed Stability of Proton Superoxide and its Superionic Transition Under High Pressure
title_short Stability of Proton Superoxide and its Superionic Transition Under High Pressure
title_sort stability of proton superoxide and its superionic transition under high pressure
topic high pressure
phase transition
superionicity
superoxides
url https://doi.org/10.1002/advs.202415387
work_keys_str_mv AT zifanwang stabilityofprotonsuperoxideanditssuperionictransitionunderhighpressure
AT wengeyang stabilityofprotonsuperoxideanditssuperionictransitionunderhighpressure
AT duckyoungkim stabilityofprotonsuperoxideanditssuperionictransitionunderhighpressure