First-principles study on crystal structures and superconductivity of ternary metal hydride La-Sr-H under high pressure

Abstract

The discovery of cage hydrides (Y,Ca)H₆, (La,Ce)H₉, and (La,Y)H₁₀ indicates the appeal of ternary hydrides as contenders for high-temperature superconductors. Herein, we systematically studied a La-Sr-H system and predicted interesting stable and metastable hydrides at 200 GPa by first-principles calculations. The results revealed that LaSrH₂₁ has a high superconducting transition temperature (T_c) of 211 K at 200 GPa, mainly attributed to its unique H₁₂ rings. LaSrH₁₂, LaSr₂H₁₈, and LaSr₃H₂₄ contain distorted H₂₄ cages and exhibit high T_c values of 160, 167, and 169 K, respectively. Notably, LaSrH₁₂ maintained dynamic stability down to 30 GPa, which is extremely low for H₂₄ cage hydrides. In addition, the T_cs of LaSrH₁₂ increased at a rate of 0.43 K/GPa with the increase in pressure. Further analysis revealed that the positive pressure-dependent T_c was mainly due to the softening of the low-frequency phonon modes and Lifshitz transition. Our work will guide the study of ternary rare- and alkaline-earth hydrides.

Keywords

High pressure / first-principles calculations / hydrides / superconductcity

References

[1] Ashcroft NW.Metallic hydrogen: a high-temperature superconductor?.Phys Rev Lett1968;21:1748-9

[2] Bardeen J,Schrieffer JR.Microscopic theory of superconductivity.Phys Rev1957;106:162-4

[3] Zhao W,Du M.Pressure-induced high-temperature superconductivity in ternary Y-Zr-H compounds.Phys Chem Chem Phys2023;25:5237-43

[4] Edalati K,Beloshenko VA.Nanomaterials by severe plastic deformation: review of historical developments and recent advances.Mater Res Lett2022;10:163-256

[5] Kang S,Liu T.A ferromagnetically coupled Fe₄₂ cyanide-bridged nanocage.Nat Commun2015;6:5955 PMCID:PMC4354210

[6] Dalladay-Simpson P,Gregoryanz E.Evidence for a new phase of dense hydrogen above 325 gigapascals.Nature2016;529:63-7

[7] Loubeyre P,Dumas P.Synchrotron infrared spectroscopic evidence of the probable transition to metal hydrogen.Nature2020;577:631-5

[8] Ashcroft NW.Hydrogen dominant metallic alloys: high temperature superconductors?.Phys Rev Lett2004;92:187002

[9] Du M,Cui T.Compressed superhydrides: the road to room temperature superconductivity.J Phys Condens Matter2022;34:173001

[10] Goncharenko I,Hanfland M.Pressure-induced hydrogen-dominant metallic state in aluminum hydride.Phys Rev Lett2008;100:045504

[11] Eremets MI,Medvedev SA,Yao Y.Superconductivity in hydrogen dominant materials: silane.Science2008;319:1506-9

[12] Pickard CJ.Ab initio random structure searching.J Phys Condens Matter2011;23:053201

[13] Wang Y,Zhu L.Crystal structure prediction via particle-swarm optimization.Phys Rev B2010;82:094116

[14] Wang Y,Zhu L.CALYPSO: a method for crystal structure prediction.Comput Phys Commun2012;183:2063-70

[15] Gao H,Han Y.Enhancing crystal structure prediction by decomposition and evolution schemes based on graph theory.Fundam Res2021;1:466-71

[16] Oganov AR.Crystal structure prediction using ab initio evolutionary techniques: principles and applications.J Chem Phys2006;124:244704

[17] Oganov AR,Valle M.How evolutionary crystal structure prediction works-and why.ACC Chem Res2011;44:227-37

[18] Lyakhov AO,Stokes HT.New developments in evolutionary structure prediction algorithm USPEX.Comput Phys Commun2013;184:1172-82

[19] Xia K,Liu C.A novel superhard tungsten nitride predicted by machine-learning accelerated crystal structure search.Sci Bull2018;63:817-24

[20] Duan D,Tian F.Pressure-induced metallization of dense (H₂S)₂H₂ with high-T_c superconductivity.Sci Rep2014;4:6968 PMCID:PMC4225546

[21] Duan D,Tian F.Pressure-induced decomposition of solid hydrogen sulfide.Phys Rev B2015;91:180502

[22] Drozdov AP,Troyan IA,Shylin SI.Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system.Nature2015;525:73-6

[23] Einaga M,Ishikawa T.Crystal structure of the superconducting phase of sulfur hydride.Nat Phys2016;12:835-8 PMCID:PMC5446087

[24] Peng F,Pickard CJ,Wu Q.Hydrogen clathrate structures in rare earth hydrides at high pressures: possible route to room-temperature superconductivity.Phys Rev Lett2017;119:107001

[25] Liu H,Hoffmann R,Hemley RJ.Potential high-T_c superconducting lanthanum and yttrium hydrides at high pressure.Proc Natl Acad Sci USA2017;114:6990-5 PMCID:PMC5502634

[26] Drozdov AP,Minkov VS.Superconductivity at 250 K in lanthanum hydride under high pressures.Nature2019;569:528-31

[27] Somayazulu M,Mishra AK.Evidence for superconductivity above 260 K in lanthanum superhydride at megabar pressures.Phys Rev Lett2019;122:027001

[28] Hong F,Shan P.Superconductivity of lanthanum superhydride investigated using the standard four-probe configuration under high pressures.Chinese Phys Lett2020;37:107401

[29] Troyan IA,Kvashnin AG.Anomalous high-temperature superconductivity in YH₆.Adv Mater2021;33:e2006832

[30] Kong P,Kuzovnikov MA.Superconductivity up to 243 K in the yttrium-hydrogen system under high pressure.Nat Commun2021;12:5075 PMCID:PMC8379216

[31] Ma L,Xie Y.High-temperature superconducting phase in clathrate calcium hydride CaH₆ up to 215 K at a pressure of 172 GPa.Phys Rev Lett2022;128:167001

[32] Jiang Q,Song H.Ternary superconducting hydrides stabilized via Th and Ce elements at mild pressures.Fundam Res2024;4:550-6 PMCID:PMC11197597

[33] Errea I,Pickard CJ.Quantum hydrogen-bond symmetrization in the superconducting hydrogen sulfide system.Nature2016;532:81-4

[34] Errea I,Monacelli L.Quantum crystal structure in the 250-kelvin superconducting lanthanum hydride.Nature2020;578:66-9

[35] Chen W,Huang X.High-temperature superconducting phases in cerium superhydride with a T_c up to 115 K below a pressure of 1 megabar.Phys Rev Lett2021;127:117001

[36] Semenok DV,Ivanova AG.Superconductivity at 161 K in thorium hydride ThH10: synthesis and properties.Mater Today2020;33:36-44

[37] Sun Y,Xie Y,Ma Y.Route to a superconducting phase above room temperature in electron-doped hydride compounds under high pressure.Phys Rev Lett2019;123:097001

[38] Zhang Z,Hutcheon MJ.Design principles for high-temperature superconductors with a hydrogen-based alloy backbone at moderate pressure.Phys Rev Lett2022;128:047001

[39] Song Y,Nakamoto Y.Stoichiometric ternary superhydride LaBeH₈ as a new template for high-temperature superconductivity at 110 K under 80 GPa.Phys Rev Lett2023;130:266001

[40] Heil C,Bachelet GB.Superconductivity in sodalite-like yttrium hydride clathrates.Phys Rev B2019;99:220502

[41] Xie H,Shao Z.High-temperature superconductivity in ternary clathrate CaYH₁₂ under high pressures.J Phys Condens Matter2019;31:245404

[42] Liang X,Wang L.Potential high- T_c superconductivity in CaYH₁₂ under pressure.Phys Rev B2019;99:100505

[43] Zhao W,Du M.Pressure-induced high-T_c superconductivity in the ternary clathrate system Y-Ca-H.Phys Rev B2022;106:014521

[44] Chen W,Semenok DV.Enhancement of superconducting properties in the La-Ce-H system at moderate pressures.Nat Commun2023;14:2660 PMCID:PMC10170082

[45] Bi J,Zhang P.Giant enhancement of superconducting critical temperature in substitutional alloy (La,Ce)H₉.Nat Commun2022;13:5952 PMCID:PMC9551097

[46] Semenok DV,Ivanova AG.Superconductivity at 253 K in lanthanum-yttrium ternary hydrides.Mater Today2021;48:18-28

[47] Ma T,Du M.High-throughput calculation for superconductivity of sodalite-like clathrate ternary hydrides MXH₁₂ at high pressure.Mater Today Phys2023;38:101233

[48] Hooper J,Shamp A.Composition and constitution of compressed strontium polyhydrides.J Phys Chem C2014;118:6433-47

[49] Wang Y,Tse JS,Ma Y.Structural morphologies of high-pressure polymorphs of strontium hydrides.Phys Chem Chem Phys2015;17:19379-85

[50] Semenok DV,Savkin IA,Oganov AR.On distribution of superconductivity in metal hydrides.Curr Opin Solid State Mater Sci2020;24:100808

[51] Tanaka K,Liu H.Electron-phonon coupling mechanisms for hydrogen-rich metals at high pressure.Phys Rev B2017;96:100502

[52] Semenok DV,Huang X.Sr-doped superionic hydrogen glass: synthesis and properties of SrH₂₂.Adv Mater2022;34:e2200924

[53] Chen Y,Lin Z.High T_c superconductivity in layered hydrides XH₁₅ (X = Ca, Sr, Y, La) under high pressures.Front Phys2022;17:63502

[54] Kresse G.Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Phys Rev B Condens Matter1996;54:11169-86

[55] Perdew JP,Ernzerhof M.Generalized gradient approximation made simple.Phys Rev Lett1996;77:3865-8

[56] Perdew JP.Pair-distribution function and its coupling-constant average for the spin-polarized electron gas.Phys Rev B Condens Matter1992;46:12947-54

[57] Blöchl PE.Projector augmented-wave method.Phys Rev B Condens Matter1994;50:17953-79

[58] Maintz S,Tchougréeff AL.LOBSTER: a tool to extract chemical bonding from plane-wave based DFT.J Comput Chem2016;37:1030-5 PMCID:PMC5067632

[59] Togo A,Tanaka I.First-principles calculations of the ferroelastic transition between rutile-type and CaCl₂-typeSiO₂ at high pressures.Phys Rev B2008;78:134106

[60] Giannozzi P,Bonini N.QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials.J Phys Condens Matter2009;21:395502

[61] Vanderbilt D.Soft self-consistent pseudopotentials in a generalized eigenvalue formalism.Phys Rev B Condens Matter1990;41:7892-5

[62] Appel J.Transition temperature of d-f -band superconductors.Phys Rev B1973;8:1079-87

[63] Wu Y,Hautier G,Ceder G.First principles high throughput screening of oxynitrides for water-splitting photocatalysts.Energy Environ Sci2013;6:157-68

[64] Hinuma Y,Kumagai Y.Discovery of earth-abundant nitride semiconductors by computational screening and high-pressure synthesis.Nat Commun2016;7:11962 PMCID:PMC4919542

[65] Song H,Cui T,Kresin VZ.High T_c superconductivity in heavy rare earth hydrides.Chinese Phys Lett2021;38:107401

[66] Lifshitz IM. Anomalies of electron characteristics in the high pressure region. 1960. Available from: https://www.osti.gov/biblio/4173345 [Last accessed on 15 Jul 2024]

[67] Yang K,Chen H,Li B.Stable structures and superconducting properties of Ca-La-H compounds under pressure.J Phys Condens Matter2022;34:355401