Strong Dependence of Point Defect Properties in Metal Halide Perovskites on Description of van der Waals Interaction.

Covalent bonding; Defect property; Electrooptical response; Halide perovskites; Ionic bonding; Optoelectronics property; Reaction pathways; Strong dependences; Van Der Waals interactions; Vibrational dynamics; Materials Science (all); Physical and Theoretical Chemistry

Abstract :

[en] Weaker than ionic and covalent bonding, van der Waals (vdW) interactions can have a significant impact on structure and function of molecules and materials, including stabilities of conformers and phases, chemical reaction pathways, electro-optical response, electron-vibrational dynamics, etc. Metal halide perovskites (MHPs) are widely investigated for their excellent optoelectronic properties, stemming largely from high defect tolerance. Although MHPs are primarily ionic compounds, we demonstrate that vdW interactions contribute ∼5% to the total energy, and that static, dynamics, electronic and optical properties of point defects in MHPs depend significantly on the vdW interaction model used. Focusing on widely studied CsPbBr3 with the common Br vacancy and interstitial defects, we compare the PBE, PBE+D3, PBE+TS, PBE+TS/HI and PBE+MBD-NL models and show that vdW interactions strongly alter the global and local geometric structure, and change the fundamental bandgap, midgap state energies and electron-vibrational coupling. The vdW interaction sensitivity stems from involvement of heavy and highly polarizable chemical elements and the soft MHP structure.

Disciplines :

Chemistry

Author, co-author :

Deng, Linjie; School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, China

Ran, Jingyi ; Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States

Wang, Bipeng ; Department of Chemical Engineering, University of Southern California, Los Angeles, California 90089, United States

BOZIKI, Ariadni ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > Department of Computer Science (DCS)

TKATCHENKO, Alexandre ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > Department of Physics and Materials Science (DPHYMS)

Jiang, Jun ; Key Laboratory of Precision and Intelligent Chemistry, Hefei National Research Center for Physical Sciences at the Microscale, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, China

Prezhdo, Oleg V ; Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States ; Department of Physics and Astronomy, University of Southern California, Los Angeles, California 90089, United States

External co-authors :

yes

Language :

English

Title :

Strong Dependence of Point Defect Properties in Metal Halide Perovskites on Description of van der Waals Interaction.

Publication date :

24 October 2024

Journal title :

Journal of Physical Chemistry Letters

eISSN :

1948-7185

Publisher :

American Chemical Society, United States

Volume :

Issue :

Pages :

10465 - 10472

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.4c02390

Funders :

China Scholarship Council
National Science Foundation

Funding text :

L. D. was financially supported by the China Scholarship Council. O. V. P. acknowledges the support of the US National Science Foundation, grant CHE-2154367.

Available on ORBilu :

since 06 November 2025

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