Inert gases (e.g., He and Xe) can exhibit chemical activity at high pressure, reacting with other substances to form compounds of unexpected chemical stoichiometry. This work combines first-principles calculations and crystal structure predictions to propose four unexpected stable compounds of CH4Xe3, (CH4)2Xe, (CH4)3Xe, and (CH4)3Xe2 at pressure ranges from 2 to 100 GPa. All structures are composed of isolated Xe atoms and CH4 molecules except for (CH4)3Xe2, which comprises a polymerization product, C3H8, and hydrogen molecules. Ab initio molecular dynamics simulations indicate that pressure plays a very important role in the different temperature driving state transitions of CH4–Xe compounds. At lower pressures, the compounds follow the state transition of solid–plastic–fluid phases with increasing temperature, while at higher pressures, the stronger Xe–C interaction induces the emergence of a superionic state for CH4Xe3 and (CH4)3Xe2 as temperature increases. These results not only expand the family of CH4–Xe compounds, they also contribute to models of the structures and evolution of planetary interiors.
REFERENCES
1.
P.
Loubeyre
, M.
Jean-Louis
, R.
LeToullec
, and L.
Charon-Gérard
, “High pressure measurements of the He–Ne binary phase diagram at 296 K: Evidence for the stability of a stoichiometric Ne(He)2 solid
,” Phys. Rev. Lett.
70
, 178
–181
(1993
).2.
A.
Dewaele
, A. D.
Rosa
, and N.
Guignot
, “Argon-neon binary diagram and ArNe2 laves phase
,” J. Chem. Phys.
151
, 124708
(2019
).3.
M.
Xu
, Y.
Li
, and Y.
Ma
, “Materials by design at high pressures
,” Chem. Sci.
13
, 329
–344
(2022
).4.
H.
Tang
, X.
Yuan
, Y.
Cheng
, H.
Fei
, F.
Liu
, T.
Liang
, Z.
Zeng
, T.
Ishii
, M.-S.
Wang
, T.
Katsura
et al, “Synthesis of paracrystalline
diamond
,” Nature
599
, 605
–610
(2021
).5.
K.
Luo
, B.
Liu
, W.
Hu
, X.
Dong
, Y.
Wang
, Q.
Huang
, Y.
Gao
, L.
Sun
, Z.
Zhao
, Y.
Wu
et al, “Coherent interfaces govern direct transformation from graphite to
diamond
,” Nature
607
, 486
–491
(2022
).6.
C.
Liu
, J.
Wang
, X.
Deng
, X.
Wang
, C. J.
Pickard
, R.
Helled
, Z.
Wu
, H.-T.
Wang
, D.
Xing
, and J.
Sun
, “Partially diffusive helium-silica compound under high pressure
,”
Chin. Phys. Lett.
39
, 076101
(2022
).7.
G.
Weck
, A.
Dewaele
, and P.
Loubeyre
, “Oxygen/noble gas binary phase diagrams at 296 K and high pressures
,” Phys. Rev. B
82
, 014112
(2010
).8.
A.
Dewaele
, P.
Loubeyre
, P.
Dumas
, and M.
Mezouar
, “Oxygen impurities reduce the metallization pressure of xenon
,” Phys. Rev. B
86
, 014103
(2012
).9.
A.
Dewaele
, N.
Worth
, C. J.
Pickard
, R. J.
Needs
, S.
Pascarelli
, O.
Mathon
, M.
Mezouar
, and T.
Irifune
, “Synthesis and stability of xenon oxides Xe2O5 and Xe3O2 under pressure
,” Nat. Chem.
8
,
784
–790
(2016
).10.
C.
Sanloup
, S. A.
Bonev
, M.
Hochlaf
, and H. E.
Maynard-Casely
, “Reactivity of xenon with ice at planetary conditions
,” Phys. Rev. Lett.
110
, 265501
(2013
).11.
C.
Sanloup
, H.-K.
Mao
, and R. J.
Hemley
, “High-pressure transformations in xenon hydrates
,” Proc. Natl. Acad. Sci. U. S. A.
99
, 25
–28
(2002
).12.
M.
Somayazulu
, P.
Dera
, A. F.
Goncharov
, S. A.
Gramsch
, P.
Liermann
, W.
Yang
, Z.
Liu
, H.-K.
Mao
, and R. J.
Hemley
, “Pressure-induced bonding and compound formation in xenon–hydrogen solids
,” Nat. Chem.
2
, 50
–53
(2010
).13.
L.
Zhu
, H.
Liu
, C. J.
Pickard
, G.
Zou
, and Y.
Ma
, “Reactions of xenon with iron and nickel are predicted in the Earth’s inner core
,” Nat. Chem.
6
, 644
(2014
).14.
F.
Peng
, X.
Song
, C.
Liu
, Q.
Li
, M.
Miao
, C.
Chen
, and Y.
Ma
, “Xenon iron oxides predicted as potential Xe hosts in Earth’s lower mantle
,” Nat. Commun.
11
, 5227
(2020
).15.
C.
Sanloup
, R. J.
Hemley
, and H. K.
Mao
, “Evidence for xenon silicates at high pressure and temperature
,” Geophys. Res. Lett.
29
, 1883
, (2002
).16.
X.
Dong
, A. R.
Oganov
, A. F.
Goncharov
, E.
Stavrou
, S.
Lobanov
, G.
Saleh
, G.-R.
Qian
, Q.
Zhu
, C.
Gatti
, V. L.
Deringer
et al, “A stable compound of helium and
sodium at high pressure
,” Nat. Chem.
9
, 440
–445
(2017
).17.
J.
Shi
, W.
Cui
, J.
Hao
, M.
Xu
, X.
Wang
, and Y.
Li
, “Formation of ammonia–helium compounds at high pressure
,” Nat. Commun.
11
, 3164
(2020
).18.
C.
Liu
, H.
Gao
, A.
Hermann
, Y.
Wang
, M.
Miao
, C. J.
Pickard
, R. J.
Needs
, H.-T.
Wang
, D.
Xing
, and J.
Sun
, “Plastic and superionic helium ammonia compounds under high pressure and high
temperature
,” Phys. Rev. X
10
, 021007
(2020
).19.
Y.
Li
, X.
Feng
, H.
Liu
, J.
Hao
, S. A. T.
Redfern
, W.
Lei
, D.
Liu
, and Y.
Ma
, “Route to high-energy density polymeric nitrogen t-N via He–N compounds
,” Nat. Commun.
9
, 722
(2018
).20.
J.
Hou
, X.-J.
Weng
, A. R.
Oganov
, X.
Shao
, G.
Gao
, X.
Dong
, H.-T.
Wang
, Y.
Tian
, and X.-F.
Zhou
, “Helium–nitrogen mixtures at high pressure
,” Phys. Rev. B
103
, L060102
(2021
).21.
H.
Liu
, Y.
Yao
, and D. D.
Klug
, “Stable structures of He and H2O at high pressure
,” Phys. Rev. B
91
, 014102
(2015
).22.
C.
Liu
, H.
Gao
, Y.
Wang
, R. J.
Needs
, C. J.
Pickard
, J.
Sun
, H.-T.
Wang
, and D.
Xing
, “Multiple superionic states in helium–water compounds
,” Nat. Phys.
15
, 1065
–1070
(2019
).23.
Y.
Bai
, Z.
Liu
, J.
Botana
, D.
Yan
, H.-Q.
Lin
, J.
Sun
, C. J.
Pickard
, R. J.
Needs
, and M.-S.
Miao
, “Electrostatic force driven helium insertion into ammonia and water crystals under pressure
,” Commun. Chem.
2
, 102
(2019
).24.
Q.
Zhu
, D. Y.
Jung
, A. R.
Oganov
, C. W.
Glass
, C.
Gatti
, and A. O.
Lyakhov
, “Stability of xenon oxides at high pressures
,” Nat. Chem.
5
, 61
–65
(2013
).25.
A.
Hermann
and P.
Schwerdtfeger
, “Xenon suboxides stable under pressure
,” J. Phys. Chem. Lett.
5
, 4336
–4342
(2014
).26.
J.
Zhang
, J.
Lv
, H.
Li
, X.
Feng
, C.
Lu
, S. A. T.
Redfern
, H.
Liu
, C.
Chen
, and Y.
Ma
, “Rare helium-bearing compound FeO2He stabilized at deep-Earth conditions
,” Phys. Rev. Lett.
121
,
255703
(2018
).27.
P.
Zhang
, J.
Shi
, W.
Cui
, C.
Liu
, S.
Ding
, K.
Yang
, J.
Hao
, and Y.
Li
, “Formation of N H3–Xe compound at the extreme condition of planetary interiors
,” Phys. Rev. B
105
, 214109
(2022
).28.
X. Z.
Yan
, Y. M.
Chen
, and H. Y.
Geng
, “Prediction of the reactivity of argon with xenon under high pressures
,” ACS Omega
4
, 13640
–13644
(2019
).29.
D. A.
Nelson
, Jr. and A. L.
Ruoff
, “Metallic xenon at static pressures
,” Phys. Rev. Lett.
42
, 383
(1979
).30.
K. S.
Chan
, T. L.
Huang
, T. A.
Grzybowski
, T. J.
Whetten
, and A. L.
Ruoff
, “Pressure present during metallization of xenon
,” Phys. Rev. B
26
, 7116
–7118
(1982
).31.
K. A.
Goettel
, J. H.
Eggert
, I. F.
Silvera
, and W. C.
Moss
, “Optical evidence for the metallization of xenon at 132(5) GPa
,” Phys. Rev. Lett.
62
, 665
–668
(1989
).32.
R.
Reichlin
, K. E.
Brister
, A. K.
McMahan
, M.
Ross
, S.
Martin
, Y. K.
Vohra
, and A. L.
Ruoff
, “Evidence for the insulator-metal transition in xenon from optical, x-ray, and band-structure studies to 170 GPa
,” Phys. Rev. Lett.
62
, 669
–672
(1989
).33.
W.
Hubbard
, “Interiors of the giant planets
,” Science
214
, 145
–149
(1981
).34.
M.
Podolak
, A.
Weizman
, and M.
Marley
, “Comparative models of Uranus and Neptune
,” Planet. Space Sci.
43
, 1517
–1522
(1995
).35.
M.
Bethkenhagen
, E. R.
Meyer
, S.
Hamel
, N.
Nettelmann
, M.
French
, L.
Scheibe
, C.
Ticknor
, L. A.
Collins
, J. D.
Kress
, J. J.
Fortney
, and R.
Redmer
, “Planetary ices and the linear mixing approximation
,” Astrophys. J.
848
, 67
(2017
).36.
N.
Teanby
, P.
Irwin
, J.
Moses
, and R.
Helled
, “Neptune and Uranus: Ice or rock giants?
,” Philos. Trans. R. Soc., A
378
, 20190489
(2020
).37.
G.
Gao
, A. R.
Oganov
, Y.
Ma
, H.
Wang
, P.
Li
, Y.
Li
, T.
Iitaka
, and G.
Zou
, “Dissociation of methane under high pressure
,” J. Chem. Phys.
133
, 144508
(2010
).38.
E.
Sugimura
, T.
Komabayashi
, K.
Ohta
, K.
Hirose
, Y.
Ohishi
, and L. S.
Dubrovinsky
, “Experimental evidence of superionic conduction in H2O ice
,” J. Chem. Phys.
137
, 194505
(2012
).39.
S.
Ninet
, F.
Datchi
, and A. M.
Saitta
, “Proton disorder and superionicity in hot dense ammonia ice
,” Phys. Rev. Lett.
108
, 165702
(2012
).40.
F.
Ancilotto
, G. L.
Chiarotti
, S.
Scandolo
, and E.
Tosatti
, “Dissociation of methane into hydrocarbons at extreme (planetary) pressure and temperature
,” Science
275
, 1288
–1290
(1997
).41.
S. J.
Kim
, C. K.
Sim
, J.
Ho
, T. R.
Geballe
, Y. L.
Yung
, S.
Miller
, and Y. H.
Kim
, “Hot CH4 in the polar regions of Jupiter
,” Icarus
257
, 217
–220
(2015
).42.
T. M.
Donahue
and R. R.
Hodges
, Jr., “Venus methane and water
,” Geophys. Res. Lett.
20
, 591
–594
, (1993
).43.
O.
Mousis
, E.
Chassefiere
, N. G.
Holm
, A.
Bouquet
, J. H.
Waite
, W. D.
Geppert
, S.
Picaud
, Y.
Aikawa
, M.
Ali-Dib
, J.-L.
Charlou
, and P.
Rousselot
, “Methane clathrates in the solar system
,” Astrobiology
15
, 308
–326
(2015
).44.
H.
Hirai
, S.-I.
Machida
, T.
Kawamura
, Y.
Yamamoto
, and T.
Yagi
, “Stabilizing of methane hydrate and transition to a new high-pressure structure at 40 GPa
,” Am. Mineral.
91
, 826
–830
(2006
).45.
H.
Kadobayashi
, H.
Hirai
, H.
Ohfuji
, M.
Ohtake
, and Y.
Yamamoto
, “In situ Raman and X-ray diffraction studies on the high pressure and temperature stability of methane hydrate up to 55 GPa
,” J. Chem. Phys.
148
, 164503
(2018
).46.
X.
Cao
, Y.
Huang
, X.
Jiang
, Y.
Su
, and J.
Zhao
, “Phase diagram of water–methane by first-principles thermodynamics: Discovery of MH-IV and MH-V hydrates
,” Phys. Chem. Chem. Phys.
19
, 15996
–16002
(2017
).47.
M.
Somayazulu
, L.
Finger
, R.
Hemley
, and H.
Mao
, “High-pressure compounds in methane–hydrogen mixtures
,” Science
271
, 1400
–1402
(1996
).48.
Y.
Liu
, D.
Duan
, F.
Tian
, X.
Huang
, D.
Li
, Z.
Zhao
, X.
Sha
, B.
Chu
, H.
Zhang
, B.
Liu
, and T.
Cui
, “Crystal
structures and properties of the CH4H2 compound under high pressure
,” RSC Adv.
4
, 37569
–37574
(2014
).49.
S.
Schaack
, U.
Ranieri
, P.
Depondt
, R.
Gaal
, W. F.
Kuhs
, P.
Gillet
, F.
Finocchi
, and L. E.
Bove
, “Observation of methane filled hexagonal ice stable up to 150 GPa
,” Proc. Natl. Acad. Sci. U. S. A.
116
, 16204
–16209
(2019
).50.
U.
Ranieri
, L. J.
Conway
, M.-E.
Donnelly
, H.
Hu
, M.
Wang
, P.
Dalladay-Simpson
, M.
Peña Alvarez
, E.
Gregoryanz
, A.
Hermann
, and R. T.
Howie
, “Formation and stability of dense
methane–hydrogen compounds
,” Phys. Rev. Lett.
128
, 215702
(2022
).51.
H.
Gao
, C.
Liu
, A.
Hermann
, R. J.
Needs
, C. J.
Pickard
, H.-T.
Wang
, D.
Xing
, and J.
Sun
, “Coexistence of plastic and partially diffusive phases in a helium–methane compound
,” Natl. Sci. Rev.
7
, 1540
–1547
(2020
).52.
E.
Anders
and T.
Owen
, “Mars and Earth: Origin and abundance of volatiles: Mars has only 3 percent of Earth’s share of volatiles, but got them from the same meteoritic source
,” Science
198
, 453
–465
(1977
).53.
P.
Mahaffy
, H.
Niemann
, A.
Alpert
, S.
Atreya
, J.
Demick
, T.
Donahue
, D.
Harpold
, and T.
Owen
, “Noble gas abundance and isotope ratios in the atmosphere of Jupiter from the Galileo Probe Mass Spectrometer
,” J. Geophys. Res.
105
,
15061
–15071
, https://doi.org/10.1029/1999je001224 (2000
).54.
T. M.
Donahue
, J.
Hoffman
, and R.
Hodges
, Jr., “Krypton and xenon in the atmosphere of venus
,” Geophys. Res. Lett.
8
, 513
–516
, https://doi.org/10.1029/gl008i005p00513 (1981
).55.
H.
Lin
, Y.-L.
Li
, Z.
Zeng
, X.-J.
Chen
, and H.
Lin
, “Structural, electronic, and dynamical properties of methane under high pressure
,” J. Chem. Phys.
134
, 064515
(2011
).56.
E.
Kim
, M.
Nicol
, H.
Cynn
, and C.-S.
Yoo
, “Martensitic fcc-to-hcp transformations in solid xenon under pressure: A first-principles study
,” Phys. Rev. Lett.
96
, 035504
(2006
).57.
Y.
Wang
, J.
Lv
, L.
Zhu
, and Y.
Ma
, “Crystal structure prediction via particle-swarm optimization
,” Phys. Rev. B
82
, 094116
(2010
).58.
Y.
Wang
, J.
Lv
, L.
Zhu
, and Y.
Ma
, “CALYPSO: A method for crystal structure prediction
,” Comput. Phys. Commun.
183
, 2063
–2070
(2012
).59.
B.
Gao
, P.
Gao
, S.
Lu
, J.
Lv
, Y.
Wang
, and Y.
Ma
, “Interface structure prediction via CALYPSO method
,” Sci. Bull.
64
, 301
–309
(2019
).60.
X.
Shao
, J.
Lv
, P.
Liu
, S.
Shao
, P.
Gao
, H.
Liu
, Y.
Wang
, and Y.
Ma
, “A symmetry-orientated divide-and-conquer method for crystal structure prediction
,” J. Chem. Phys.
156
, 014105
(2022
).61.
W.
Cui
and Y.
Li
, “The role of CALYPSO in the discovery of high-Tc hydrogen-rich superconductors
,” Chin. Phys. B
28
, 107104
(2019
).62.
W.
Cui
, T.
Bi
, J.
Shi
, Y.
Li
, H.
Liu
, E.
Zurek
, and R. J.
Hemley
, “Route to high-Tc superconductivity via CH4-intercalated H3S hydride perovskites
,” Phys. Rev. B
101
, 134504
(2020
).63.
B.
Liu
, W.
Cui
, J.
Shi
, L.
Zhu
, J.
Chen
, S.
Lin
, R.
Su
, J.
Ma
, K.
Yang
, M.
Xu
et al, “Effect of covalent bonding on the superconducting critical temperature
of the H-S-Se system
,” Phys. Rev. B
98
, 174101
(2018
).64.
J.
Chen
, W.
Cui
, K.
Gao
, J.
Hao
, J.
Shi
, and Y.
Li
, “Pressure-stabilized unconventional stoichiometric yttrium sulfides
,” Phys. Rev. Res.
2
, 043435
(2020
).65.
S.
Ding
, J.
Shi
, J.
Xie
, W.
Cui
, P.
Zhang
, K.
Yang
, J.
Hao
, L.
Zhang
, and Y.
Li
, “Helium incorporation induced direct-gap silicides
,” npj Comput. Mater.
7
, 89
(2021
).66.
K.
Gao
, W.
Cui
, J.
Chen
, Q.
Wang
, J.
Hao
, J.
Shi
, C.
Liu
, S.
Botti
, M. A. L.
Marques
, and Y.
Li
, “Superconducting hydrogen tubes in hafnium hydrides at high
pressure
,” Phys. Rev. B
104
, 214511
(2021
).67.
S.
Ding
, P.
Zhang
, K.
Yang
, C.
Liu
, J.
Hao
, W.
Cui
, J.
Shi
, and Y.
Li
, “Formation of solid SiO2–He compound at high pressure and high temperature
,” Phys. Rev. B
106
, 024102
(2022
).68.
K.
Gao
, W.
Cui
, Q.
Wang
, J.
Hao
, J.
Shi
, S.
Botti
, M. A. L.
Marques
, and Y.
Li
, “Superconductivity in S-rich phases of lanthanum sulfide under high pressure
,” Phys. Rev. Mater.
6
, 064801
(2022
).69.
M.
Xu
, C.
Huang
, Y.
Li
, S.
Liu
, X.
Zhong
, P.
Jena
, E.
Kan
, and Y.
Wang
, “Electrical control of magnetic phase transition in a type-I multiferroic double-metal trihalide monolayer
,” Phys. Rev. Lett.
124
, 067602
(2020
).70.
G.
Kresse
and J.
Furthmüller
, “Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
,” Phys. Rev. B
54
, 11169
(1996
).71.
G.
Kresse
and J.
Furthmüller
, “Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
,” Comput. Mater. Sci.
6
, 15
–50
(1996
).72.
J. P.
Perdew
, J. A.
Chevary
, S. H.
Vosko
, K. A.
Jackson
, M. R.
Pederson
, D. J.
Singh
, and C.
Fiolhais
, “Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
,” Phys. Rev. B
46
, 6671
(1992
).73.
J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, “Generalized gradient approximation made simple
,” Phys. Rev. Lett.
77
, 3865
(1996
).74.
G.
Kresse
and D.
Joubert
, “From ultrasoft pseudopotentials to the projector augmented-wave method
,” Phys. Rev. B
59
, 1758
(1999
).75.
P.
Blaha
, K.
Schwarz
, P.
Sorantin
, and S.
Trickey
, “Full-potential, linearized augmented plane wave programs for crystalline systems
,” Comput. Phys. Commun.
59
, 399
–415
(1990
).76.
A.
Togo
, F.
Oba
, and I.
Tanaka
, “First-principles calculations of the ferroelastic transition between rutile-type and CaCl2-type SiO2 at high pressures
,” Phys. Rev. B
78
, 134106
(2008
).77.
S.
Nosé
, “A unified formulation of the constant temperature molecular dynamics methods
,” J. Chem. Phys.
81
, 511
–519
(1984
).78.
W. G.
Hoover
, “Canonical dynamics: Equilibrium phase-space distributions
,” Phys. Rev. A
31
, 1695
(1985
).79.
K.
Momma
and F.
Izumi
, “VESTA3 for three-dimensional visualization of crystal, volumetric and morphology data
,” J. Appl. Crystallogr.
44
, 1272
–1276
(2011
).80.
S.
Grimme
, S.
Ehrlich
, and L.
Goerigk
, “Effect of the damping function in dispersion corrected density functional theory
,” J. Comput. Chem.
32
, 1456
–1465
(2011
).81.
T. T.
Bucko
, S.
Lebegue
, J.
Hafner
, and J. G.
Angyan
, “Improved density dependent correction for the description of london dispersion forces
,” J. Chem. Theory Comput.
9
, 4293
–4299
(2013
).82.
M.
Bykov
, E.
Bykova
, C. J.
Pickard
, M.
Martinez-Canales
, K.
Glazyrin
, J. S.
Smith
, and A. F.
Goncharov
, “Structural and vibrational properties of methane up to 71 GPa
,” Phys. Rev. B
104
, 184105
(2021
).83.
J.
Sun
, A.
Ruzsinszky
, and J. P.
Perdew
, “Strongly constrained and appropriately normed semilocal density functional
,” Phys. Rev. Lett.
115
, 036402
(2015
).84.
J.
Sun
, R. C.
Remsing
, Y.
Zhang
, Z.
Sun
, A.
Ruzsinszky
, H.
Peng
, Z.
Yang
, A.
Paul
, U.
Waghmare
, X.
Wu
et al, “Accurate first-principles structures and
energies of diversely bonded systems from an efficient density functional
,” Nat. Chem.
8
, 831
–836
(2016
).85.
R.
Redmer
, T. R.
Mattsson
, N.
Nettelmann
, and M.
French
, “The phase diagram of water and the magnetic fields of Uranus and Neptune
,” Icarus
211
, 798
–803
(2011
).86.
A.
Aitta
, “Venus’ internal structure, temperature and core composition
,” Icarus
218
, 967
–974
(2012
).87.
W. B.
Hubbard
and B.
Militzer
, “A preliminary Jupiter model
,” The Astrophysical Journal
820
, 80
(2016
).© 2024 Author(s). Published under an exclusive license by AIP Publishing.
2024
Author(s)
You do not currently have access to this content.
