Charge density wave instability below the semimetal to semiconductor transition in Mo8O23

The semimetallic to semiconductor transition of a complex oxide, Mo8⁢O23, remains a mysterious process among low-dimensional conductors. Although a general agreement was reached that the transition originates from a purely structural tilt instability related to the M3 instability of perovskites, rec...

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Detalles Bibliográficos
Autores: Pouget, Jean-Paul, Guster, Bogdan, Canadell, Enric
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/394433
Acceso en línea:http://hdl.handle.net/10261/394433
Access Level:acceso abierto
Palabra clave:Charge density waves
Electrical conductivity
Electronic structure
Fermi surface
Peierls transition
Descripción
Sumario:The semimetallic to semiconductor transition of a complex oxide, Mo8⁢O23, remains a mysterious process among low-dimensional conductors. Although a general agreement was reached that the transition originates from a purely structural tilt instability related to the M3 instability of perovskites, recent scanning tunneling microscopy as well as Raman/IR reflectivity measurements have cast doubt about this scenario. We report an in-depth analysis of the density functional theory electron-hole response of this material, showing that a consistent scenario for the evolution of its structural and physical properties can not be put forward without taking into account an electron-hole instability at Γ of the perovskite fragment of the structure. We propose that the mechanism of the semimetallic to semiconductor transition involves several order parameters: (i) an octahedral tilt instability (tilt) driving the incommensurate and later commensurate modulations, and (ii) a Γ electron-hole instability coupled with the lattice via a low-frequency Raman mode. The latter induces the uniform deformation (i.e., tetramerization) of a group of four corner-sharing MoO6 octahedra (unif) repeating along one of the directions of the lattice. The two order parameters are of different symmetries and are independent in the semimetallic state but couple when the inversion symmetry is lost in the semiconducting state and the Raman mode becomes polar. The development of the uniform order of octahedral tetramers competes with the electronic and structural degrees of freedom of the high-temperature staggered tilt wave and induces a disorder of tetramer orientations stopping the growth of the charge density wave (CDW) coherence below 200 K. It is proposed that the generated polar orientation disorder can be explained by the formation of a series of solitons and antisolitons in the CDW, evidenced by a strong optical response.