Anharmonic Lattice Dynamics in Sodium Ion Conductors

被引:15
作者
Brenner, Thomas M. [1 ]
Grumet, Manuel [2 ]
Till, Paul [3 ]
Asher, Maor [1 ]
Zeier, Wolfgang G. [3 ]
Egger, David A. [2 ]
Yaffe, Omer [1 ]
机构
[1] Weizmann Inst Sci, Dept Chem & Biol Phys, IL-76100 Rehovot, Israel
[2] Tech Univ Munich, Dept Phys, D-85748 Garching, Germany
[3] Univ Munster, Inst Inorgan & Analyt Chem, D-48149 Munster, Germany
关键词
INTERATOMIC FORCE-CONSTANTS; TOTAL-ENERGY CALCULATIONS; PADDLE-WHEEL MECHANISM; SUPERIONIC CONDUCTIVITY; PHASE-TRANSITIONS; DISORDER; TEMPERATURE; DISPLACIVE; CS2NANDCL6; DIFFUSION;
D O I
10.1021/acs.jpclett.2c00904
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We employ terahertz-range temperature-dependent Raman spectroscopy and first-principles lattice dynamical calculations to show that the undoped sodium ion conductors Na3PS4 and isostructural Na3PSe4 both exhibit anharmonic lattice dynamics. The anharmonic effects in the compounds involve coupled host lattice-Na+ ion dynamics that drive the tetragonal-to-cubic phase transition in both cases, but with a qualitative difference in the anharmonic character of the transition. Na3PSe4 shows an almost purely displacive character with the soft modes disappearing in the cubic phase as the change in symmetry shifts these modes to the Raman-inactive Brillouin zone boundary. Na3PS4 instead shows an order-disorder character in the cubic phase, with the soft modes persisting through the phase transition and remaining Raman active in the cubic phase, violating Raman selection rules for that phase. Our findings highlight the important role of coupled host lattice-mobile ion dynamics in vibrational instabilities that are coincident with the exceptional conductivity of these Na+ ion conductors.
引用
收藏
页码:5938 / 5945
页数:8
相关论文
共 57 条
[21]   Linear optical properties in the projector-augmented wave methodology -: art. no. 045112 [J].
Gajdos, M ;
Hummer, K ;
Kresse, G ;
Furthmüller, J ;
Bechstedt, F .
PHYSICAL REVIEW B, 2006, 73 (04)
[22]   INTERATOMIC FORCE-CONSTANTS FROM FIRST PRINCIPLES - THE CASE OF ALPHA-QUARTZ [J].
GONZE, X ;
CHARLIER, JC ;
ALLAN, DC ;
TETER, MP .
PHYSICAL REVIEW B, 1994, 50 (17) :13035-13038
[23]   Dynamical matrices, born effective charges, dielectric permittivity tensors, and interatomic force constants from density-functional perturbation theory [J].
Gonze, X ;
Lee, C .
PHYSICAL REVIEW B, 1997, 55 (16) :10355-10368
[24]   THERMODYNAMIC PROPERTIES OF ELPASOLITES CS2NANDCL6 AND CS2NAPRCL6 [J].
GOREV, MV ;
MISYUL, SV ;
BOVINA, AF ;
ISKORNEV, IM ;
KOKOV, IT ;
FLEROV, IN .
JOURNAL OF PHYSICS C-SOLID STATE PHYSICS, 1986, 19 (14) :2441-2447
[25]   Fast Na diffusion and anharmonic phonon dynamics in superionic Na3PS4 [J].
Gupta, Mayanak K. ;
Ding, Jingxuan ;
Osti, Naresh C. ;
Abernathy, Douglas L. ;
Arnold, William ;
Wang, Hui ;
Hood, Zachary ;
Delaire, Olivier .
ENERGY & ENVIRONMENTAL SCIENCE, 2021, 14 (12) :6554-6563
[26]   A sodium-ion sulfide solid electrolyte with unprecedented conductivity at room temperature [J].
Hayashi, A. ;
Masuzawa, N. ;
Yubuchi, S. ;
Tsuji, F. ;
Hotehama, C. ;
Sakuda, A. ;
Tatsumisago, M. .
NATURE COMMUNICATIONS, 2019, 10 (1)
[27]   VOLUME EFFECT OR PADDLE-WHEEL MECHANISM - FAST ALKALI-METAL IONIC-CONDUCTION IN SOLIDS WITH ROTATIONALLY DISORDERED COMPLEX ANIONS [J].
JANSEN, M .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (12) :1547-1558
[28]   SOFT MODE AND STRUCTURAL PHASE-TRANSITION IN THE CUBIC ELPASOLITE CS2NANDCL6 [J].
KNUDSEN, GP .
SOLID STATE COMMUNICATIONS, 1984, 49 (11) :1045-1047
[29]   Comparing the Descriptors for Investigating the Influence of Lattice Dynamics on Ionic Transport Using the Superionic Conductor Na3PS4-xSex [J].
Krauskopf, Thorben ;
Muy, Sokseiha ;
Culver, Sean P. ;
Ohno, Saneyuki ;
Delaire, Olivier ;
Shao-Horn, Yang ;
Zeier, Wolfgang G. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (43) :14464-14473
[30]   Local Tetragonal Structure of the Cubic Superionic Conductor Na3PS4 [J].
Krauskopf, Thorben ;
Culver, Sean P. ;
Zeier, Wolfgang G. .
INORGANIC CHEMISTRY, 2018, 57 (08) :4739-4744