Ca2 Mn O4 structural path: Following the negative thermal expansion at the local scale

Pedro Rocha-Rodrigues; Samuel S.M. Santos; Gonçalo N.P. Oliveira; Tiago Leal; Ivan P. Miranda; António M. Dos Santos; João G. Correia; Lucy V.C. Assali; Helena M. Petrilli; João P. Araújo; Armandina M.L. Lopes

doi:10.1103/PhysRevB.102.104115

Ca2 Mn O4 structural path: Following the negative thermal expansion at the local scale

Pedro Rocha-Rodrigues, Samuel S.M. Santos, Gonçalo N.P. Oliveira, Tiago Leal, Ivan P. Miranda, António M. Dos Santos, João G. Correia, Lucy V.C. Assali, Helena M. Petrilli, João P. Araújo, Armandina M.L. Lopes

Materials Engineering

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The oxygen octahedral rotations in Ca2MnO4, the first member of the CaO(CaMnO3)n Ruddlesden-Popper family, is probed through a set of complementary techniques, including temperature-dependent neutron and x-ray diffraction, combined with local probe studies and ab initio calculations. Here we demonstrate the enhancement of the uniaxial negative thermal expansion coefficient from -1.26±0.25 to -21±1.8 ppm/K at the second order I41/acd to I4/mmm structural phase transition, providing direct evidence for the corkscrew atomic mechanism. We establish, also, that the predicted I4/mmm high symmetry is attained around 1050 K. At lower temperatures, within the 10-1000 K temperature range, our first-principles calculations and detailed analysis of the Ca local environment reveals that the reported Aba2 structural phase, coexisting with the I41/acd one, cannot describe correctly this compound. On the other hand, our data allow for the coexistence of the locally identical I41/acd and Acam structural phases.

Original language	English
Article number	104115
Journal	Physical Review B
Volume	102
Issue number	10
DOIs	https://doi.org/10.1103/PhysRevB.102.104115
State	Published - Sep 2020

Funding

The authors acknowledge the support of Juliana Schell and Karl Johnston during beamtime at ISOLDE-CERN. The authors acknowledge project NECL (Network of Extreme Conditions Laboratories) under NORTE-01-0145-FEDER-022096, POCI-01-0145-FEDER-029454, and POCI-01-0145-FEDER-032527, and FCT through EXPL/IF/00686/2014 602, CERN/FIS-PAR/0005/2017, UIDB/04968/2020 and UIDP/04968/2020. The authors also acknowledge funding from FAPESP Project 2018/07760-4, the German Federal Ministry of Education and Research (BMBF) through Contract No. 05K16PGA and the European Commission through the Horizon 2020 program Grants No. 734801 and No. 262010 (ENSAR2, for supporting IS647 ISOLDE-CERN experiment). We also acknowledge support from CAPES. L.V.C.A. (Project No.305753/2017-7) and H.M.P. (Project No. 311373/2018-6) also acknowledge funding from CNPq. A portion of this research used resources at the Spallation Neutron Source, and the Center for Nanophase Materials Sciences, both DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory, USA. Computational resources at the Brazilian National Computing Laboratory (LNCC) have been used. P.R.-R. acknowledges support from UE, FSE and FCT-Portugal through the Grant SFRH/BD/117448/2016.

Funders	Funder number
Extreme Conditions Laboratories	POCI-01-0145-FEDER-029454, POCI-01-0145-FEDER-032527, NORTE-01-0145-FEDER-022096
Fundação de Amparo à Pesquisa do Estado de São Paulo
Fundação para a Ciência e a Tecnologia	UIDP/04968/2020, EXPL/IF/00686/2014 602, CERN/FIS-PAR/0005/2017, UIDB/04968/2020
Fundação para a Ciência e a Tecnologia

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Rocha-Rodrigues, P., Santos, S. S. M., Oliveira, G. N. P., Leal, T., Miranda, I. P., Dos Santos, A. M., Correia, J. G., Assali, L. V. C., Petrilli, H. M., Araújo, J. P., & Lopes, A. M. L. (2020). Ca2 Mn O4 structural path: Following the negative thermal expansion at the local scale. Physical Review B, 102(10), Article 104115. https://doi.org/10.1103/PhysRevB.102.104115

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title = "Ca2 Mn O4 structural path: Following the negative thermal expansion at the local scale",

abstract = "The oxygen octahedral rotations in Ca2MnO4, the first member of the CaO(CaMnO3)n Ruddlesden-Popper family, is probed through a set of complementary techniques, including temperature-dependent neutron and x-ray diffraction, combined with local probe studies and ab initio calculations. Here we demonstrate the enhancement of the uniaxial negative thermal expansion coefficient from -1.26±0.25 to -21±1.8 ppm/K at the second order I41/acd to I4/mmm structural phase transition, providing direct evidence for the corkscrew atomic mechanism. We establish, also, that the predicted I4/mmm high symmetry is attained around 1050 K. At lower temperatures, within the 10-1000 K temperature range, our first-principles calculations and detailed analysis of the Ca local environment reveals that the reported Aba2 structural phase, coexisting with the I41/acd one, cannot describe correctly this compound. On the other hand, our data allow for the coexistence of the locally identical I41/acd and Acam structural phases.",

author = "Pedro Rocha-Rodrigues and Santos, {Samuel S.M.} and Oliveira, {Gon{\c c}alo N.P.} and Tiago Leal and Miranda, {Ivan P.} and {Dos Santos}, {Ant{\'o}nio M.} and Correia, {Jo{\~a}o G.} and Assali, {Lucy V.C.} and Petrilli, {Helena M.} and Ara{\'u}jo, {Jo{\~a}o P.} and Lopes, {Armandina M.L.}",

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year = "2020",

month = sep,

doi = "10.1103/PhysRevB.102.104115",

language = "English",

volume = "102",

journal = "Physical Review B",

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T2 - Following the negative thermal expansion at the local scale

AU - Rocha-Rodrigues, Pedro

AU - Santos, Samuel S.M.

AU - Oliveira, Gonçalo N.P.

AU - Leal, Tiago

AU - Miranda, Ivan P.

AU - Dos Santos, António M.

AU - Correia, João G.

AU - Assali, Lucy V.C.

AU - Petrilli, Helena M.

AU - Araújo, João P.

AU - Lopes, Armandina M.L.

PY - 2020/9

Y1 - 2020/9

N2 - The oxygen octahedral rotations in Ca2MnO4, the first member of the CaO(CaMnO3)n Ruddlesden-Popper family, is probed through a set of complementary techniques, including temperature-dependent neutron and x-ray diffraction, combined with local probe studies and ab initio calculations. Here we demonstrate the enhancement of the uniaxial negative thermal expansion coefficient from -1.26±0.25 to -21±1.8 ppm/K at the second order I41/acd to I4/mmm structural phase transition, providing direct evidence for the corkscrew atomic mechanism. We establish, also, that the predicted I4/mmm high symmetry is attained around 1050 K. At lower temperatures, within the 10-1000 K temperature range, our first-principles calculations and detailed analysis of the Ca local environment reveals that the reported Aba2 structural phase, coexisting with the I41/acd one, cannot describe correctly this compound. On the other hand, our data allow for the coexistence of the locally identical I41/acd and Acam structural phases.

AB - The oxygen octahedral rotations in Ca2MnO4, the first member of the CaO(CaMnO3)n Ruddlesden-Popper family, is probed through a set of complementary techniques, including temperature-dependent neutron and x-ray diffraction, combined with local probe studies and ab initio calculations. Here we demonstrate the enhancement of the uniaxial negative thermal expansion coefficient from -1.26±0.25 to -21±1.8 ppm/K at the second order I41/acd to I4/mmm structural phase transition, providing direct evidence for the corkscrew atomic mechanism. We establish, also, that the predicted I4/mmm high symmetry is attained around 1050 K. At lower temperatures, within the 10-1000 K temperature range, our first-principles calculations and detailed analysis of the Ca local environment reveals that the reported Aba2 structural phase, coexisting with the I41/acd one, cannot describe correctly this compound. On the other hand, our data allow for the coexistence of the locally identical I41/acd and Acam structural phases.

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Ca2 Mn O4 structural path: Following the negative thermal expansion at the local scale

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