Fluctuations and Anharmonicity in Lead Iodide Perovskites from Molecular Dynamics Supercell Simulationss

Handle URI:
http://hdl.handle.net/10754/625455
Title:
Fluctuations and Anharmonicity in Lead Iodide Perovskites from Molecular Dynamics Supercell Simulationss
Authors:
Carignano, Marcelo Andrés; Aravindh, S. Assa; Roqan, Iman S. ( 0000-0001-7442-4330 ) ; Even, Jacky; Katan, Claudine
Abstract:
We present a systematic study based on first principles molecular dynamics simulations of lead iodide perovskites with three different cations, including methylammonium (MA), formamidinium (FA) and cesium. Using the high temperature perovskite structure as a reference, we investigate the instabilities that develop as the material is cooled down to 370 K. All three perovskites display anharmonicity in the motion of the iodine atoms, with the stronger effect observed for the MAPbI$_3$ and CsPbI$_3$. At high temperature, this behavior can be traced back to the reduced effective size of the Cs$^+$ and MA$^+$ cations. MAPbI$_3$ undergoes a spontaneous phase transition within our simulation model driven by the dipolar interaction between neighboring MA cations as the temperature is decreased from 450 K. The reverse transformation from tetragonal to cubic is also monitored through the large distribution of the octahedral tilting angles accompanied by an increase in the anharmonicity of the iodine atoms motion. Both MA and FA hybrid perovskites show a strong coupling between the molecular orientations and the local lattice deformations, suggesting mixed order-disorder/displacive characters of the high temperature phase transitions.
KAUST Department:
Physical Sciences and Engineering (PSE) Division
Citation:
Carignano MA, Aravindh SA, Roqan IS, Even J, Katan C (2017) Fluctuations and Anharmonicity in Lead Iodide Perovskites from Molecular Dynamics Supercell Simulationss. The Journal of Physical Chemistry C. Available: http://dx.doi.org/10.1021/acs.jpcc.7b08220.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
Issue Date:
5-Sep-2017
DOI:
10.1021/acs.jpcc.7b08220
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
For computer time, this research used the resources of the Supercomputing Laboratory at the King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia and Research Computing group in Texas A&M University at Qatar. Research Computing is funded by the Qatar Foundation for Education, Science and Community Development. M. A. Carignano held an invited position at the University of Rennes 1, which is gratefully acknowledged.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.7b08220
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorCarignano, Marcelo Andrésen
dc.contributor.authorAravindh, S. Assaen
dc.contributor.authorRoqan, Iman S.en
dc.contributor.authorEven, Jackyen
dc.contributor.authorKatan, Claudineen
dc.date.accessioned2017-09-14T06:03:52Z-
dc.date.available2017-09-14T06:03:52Z-
dc.date.issued2017-09-05en
dc.identifier.citationCarignano MA, Aravindh SA, Roqan IS, Even J, Katan C (2017) Fluctuations and Anharmonicity in Lead Iodide Perovskites from Molecular Dynamics Supercell Simulationss. The Journal of Physical Chemistry C. Available: http://dx.doi.org/10.1021/acs.jpcc.7b08220.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/acs.jpcc.7b08220en
dc.identifier.urihttp://hdl.handle.net/10754/625455-
dc.description.abstractWe present a systematic study based on first principles molecular dynamics simulations of lead iodide perovskites with three different cations, including methylammonium (MA), formamidinium (FA) and cesium. Using the high temperature perovskite structure as a reference, we investigate the instabilities that develop as the material is cooled down to 370 K. All three perovskites display anharmonicity in the motion of the iodine atoms, with the stronger effect observed for the MAPbI$_3$ and CsPbI$_3$. At high temperature, this behavior can be traced back to the reduced effective size of the Cs$^+$ and MA$^+$ cations. MAPbI$_3$ undergoes a spontaneous phase transition within our simulation model driven by the dipolar interaction between neighboring MA cations as the temperature is decreased from 450 K. The reverse transformation from tetragonal to cubic is also monitored through the large distribution of the octahedral tilting angles accompanied by an increase in the anharmonicity of the iodine atoms motion. Both MA and FA hybrid perovskites show a strong coupling between the molecular orientations and the local lattice deformations, suggesting mixed order-disorder/displacive characters of the high temperature phase transitions.en
dc.description.sponsorshipFor computer time, this research used the resources of the Supercomputing Laboratory at the King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia and Research Computing group in Texas A&M University at Qatar. Research Computing is funded by the Qatar Foundation for Education, Science and Community Development. M. A. Carignano held an invited position at the University of Rennes 1, which is gratefully acknowledged.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jpcc.7b08220en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.7b08220.en
dc.titleFluctuations and Anharmonicity in Lead Iodide Perovskites from Molecular Dynamics Supercell Simulationssen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.eprint.versionPost-printen
dc.contributor.institutionQatar Environment and Energy Research Institute, Hamad bin Khalifa University, P.O. Box 5825, Doha, Qataren
dc.contributor.institutionFOTON, UMR6082, CNRS, INSA de Rennes, Avenue des Buttes de Co¨esmes, 35708 Rennes, Franceen
dc.contributor.institutionInstitut des Sciences Chimiques de Rennes, UMR6226, CNRS, Universit´e de Rennes 1, Ecole Nationale Sup´erieure de Chimie de Rennes, INSA de Rennes, 35042 Rennes Cedex, Franceen
kaust.authorAravindh, S. Assaen
kaust.authorRoqan, Iman S.en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.