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First-Principles Molecular Dynamics in Metal-Halide Perovskites: Contrasting Generalized Gradient Approximation and Hybrid Functionals

Kaiser, Waldemar and Carignano, Marcelo and Alothman, Asma A. and Mosconi, Edoardo and Kachmar, Ali and Goddard, William A., III and De Angelis, Filippo (2021) First-Principles Molecular Dynamics in Metal-Halide Perovskites: Contrasting Generalized Gradient Approximation and Hybrid Functionals. Journal of Physical Chemistry Letters, 12 (49). pp. 11886-11893. ISSN 1948-7185. doi:10.1021/acs.jpclett.1c03428.

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First-principles molecular dynamics (FPMD) represents a valuable tool to probe dynamical properties of metal-halide perovskites (MHPs) which are key to their success in optoelectronic devices. Most FPMD studies rely on generalized gradient approximation (GGA) functionals for computational efficiency matters, while hybrid functionals, although computationally demanding, are usually needed to accurately describe structural and electronic properties of MHPs. This Letter reports FPMD simulations on CsPbI₃ based on the hybrid PBE0 functional. Our results demonstrate that PBE0 leads to lattice parameters and phonon modes in excellent agreement with experimental data, while GGA results overestimate the lattice parameter and the electronic band gap and underestimate the phonon energies. Our FPMD results also shed light on anharmonic effects and double-well instabilities in the octahedral tilting, highlighting a lowered free energy barrier for PBE0 and farther separated potential wells. Our results suggest that hybrid functionals are required to accurately describe crystal structure, lattice dynamics, and anharmonicity in MHPs.

Item Type:Article
Related URLs:
URLURL TypeDescription
Kaiser, Waldemar0000-0001-9069-690X
Carignano, Marcelo0000-0001-8345-7724
Alothman, Asma A.0000-0002-4701-5424
Mosconi, Edoardo0000-0001-5075-6664
Kachmar, Ali0000-0003-2607-0819
Goddard, William A., III0000-0003-0097-5716
De Angelis, Filippo0000-0003-3833-1975
Additional Information:© 2021 American Chemical Society. Received: October 19, 2021; Accepted: December 3, 2021; Published: December 7, 2021. The Ministero dell’Istruzione dell’Università e della Ricerca (MIUR) and Università degli Studi di Perugia are acknowledged for financial support through the program “Dipartimenti di Eccellenza 2018–2022” (Grant AMIS) to F.D.A. This research was funded by PON Project “Tecnologia per celle solari bifacciali ad alta Efficienza a 4 terminali per utility scale” (BEST-4U), of the Italian Ministry MIUR (CUP B88D19000160005). W.A.G. received support from the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. A.K. acknowledges stimulating discussions with Feliciano Giustino and Samuel Poncé. E.M. and A.A.A. wish to thank the Distinguished Scientist Fellowship Program (DSFP) of King Saud University, Riyadh, Saudi Arabia. The authors declare no competing financial interest.
Group:Liquid Sunlight Alliance
Funding AgencyGrant Number
Università degli Studi di PerugiaDipartimenti di Eccellenza 2018–2022
Ministero dell'Istruzione, dell'Università e della Ricerca (MIUR)CUP B88D19000160005
Department of Energy (DOE)DE-SC0021266
King Saud UniversityUNSPECIFIED
Subject Keywords:Iodine, Free energy, Lattices, Energy levels, Computational chemistry
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Issue or Number:49
Record Number:CaltechAUTHORS:20211208-560288000
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Official Citation:First-Principles Molecular Dynamics in Metal-Halide Perovskites: Contrasting Generalized Gradient Approximation and Hybrid Functionals. Waldemar Kaiser, Marcelo Carignano, Asma A. Alothman, Edoardo Mosconi, Ali Kachmar, William A. Goddard, and Filippo De Angelis. The Journal of Physical Chemistry Letters 2021 12 (49), 11886-11893; DOI: 10.1021/acs.jpclett.1c03428
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112283
Deposited By: George Porter
Deposited On:10 Dec 2021 22:57
Last Modified:11 Nov 2022 19:22

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