Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics

Andrei Buin; Riccardo Comin; Alexander H. Ip; Edward H. Sargent

doi:10.1021/acs.jpcc.5b03613

Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics

Andrei Buin, Riccardo Comin, Alexander H. Ip, Edward H. Sargent

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

26 Scopus citations

Abstract

© 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention at both the experimental and theoretical levels. Much of this work has been dedicated to bulk material studies, yet recent experimental work has shown the formation of highly efficient quantum-confined nanocrystals with tunable band edges. Here we investigate perovskite quantum dots from theory, predicting an upper bound of the Bohr radius of 45 Å that agrees well with literature values. When the quantum dots are stoichiometric, they are trap-free and have nearly symmetric contributions to confinement from the valence and conduction bands. We further show that surface-associated conduction bandedge states in perovskite nanocrystals lie below the bulk states, which could explain the difference in Urbach tails between mesoporous and planar perovskite films. In addition to conventional molecular dynamics (MD), we implement an enhanced phase-space sampling algorithm, replica exchange molecular dynamics (REMD). We find that in simulation of methylammonium orientation and global minima, REMD outperforms conventional MD. To the best of our knowledge, this is the first REMD implementation for realistic-sized systems in the realm of DFT calculations.

Original language	English (US)
Pages (from-to)	13965-13971
Number of pages	7
Journal	The Journal of Physical Chemistry C
Volume	119
Issue number	24
DOIs	https://doi.org/10.1021/acs.jpcc.5b03613
State	Published - Jun 8 2015
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-11-009-21
Acknowledgements: This publication is based in part on work supported by Award KUS-11-009-21, made by King Abdullah University of Science and Technology (KAUST), by the Ontario Research Fund Research Excellence Program, and by the Natural Sciences and Engineering Research Council (NSERC) of Canada. Computations were performed on the Southern Ontario Smart Computing Innovation Platform (SOSCIP) Blue Gene/Q supercomputer located at the University of Toronto’s SciNet(50) HPC facility. The SOSCIP multiuniversity/industry consortium is funded by the Ontario Government, and the Federal SciNet is funded by the Canada Foundation for Innovation under the auspices of Compute Canada; the Government of Ontario; Ontario Research Fund—Research Excellence; and the University of Toronto.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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title = "Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics",

abstract = "{\textcopyright} 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention at both the experimental and theoretical levels. Much of this work has been dedicated to bulk material studies, yet recent experimental work has shown the formation of highly efficient quantum-confined nanocrystals with tunable band edges. Here we investigate perovskite quantum dots from theory, predicting an upper bound of the Bohr radius of 45 {\AA} that agrees well with literature values. When the quantum dots are stoichiometric, they are trap-free and have nearly symmetric contributions to confinement from the valence and conduction bands. We further show that surface-associated conduction bandedge states in perovskite nanocrystals lie below the bulk states, which could explain the difference in Urbach tails between mesoporous and planar perovskite films. In addition to conventional molecular dynamics (MD), we implement an enhanced phase-space sampling algorithm, replica exchange molecular dynamics (REMD). We find that in simulation of methylammonium orientation and global minima, REMD outperforms conventional MD. To the best of our knowledge, this is the first REMD implementation for realistic-sized systems in the realm of DFT calculations.",

author = "Andrei Buin and Riccardo Comin and Ip, {Alexander H.} and Sargent, {Edward H.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-11-009-21 Acknowledgements: This publication is based in part on work supported by Award KUS-11-009-21, made by King Abdullah University of Science and Technology (KAUST), by the Ontario Research Fund Research Excellence Program, and by the Natural Sciences and Engineering Research Council (NSERC) of Canada. Computations were performed on the Southern Ontario Smart Computing Innovation Platform (SOSCIP) Blue Gene/Q supercomputer located at the University of Toronto{\textquoteright}s SciNet(50) HPC facility. The SOSCIP multiuniversity/industry consortium is funded by the Ontario Government, and the Federal SciNet is funded by the Canada Foundation for Innovation under the auspices of Compute Canada; the Government of Ontario; Ontario Research Fund—Research Excellence; and the University of Toronto. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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AU - Comin, Riccardo

AU - Ip, Alexander H.

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N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-11-009-21 Acknowledgements: This publication is based in part on work supported by Award KUS-11-009-21, made by King Abdullah University of Science and Technology (KAUST), by the Ontario Research Fund Research Excellence Program, and by the Natural Sciences and Engineering Research Council (NSERC) of Canada. Computations were performed on the Southern Ontario Smart Computing Innovation Platform (SOSCIP) Blue Gene/Q supercomputer located at the University of Toronto’s SciNet(50) HPC facility. The SOSCIP multiuniversity/industry consortium is funded by the Ontario Government, and the Federal SciNet is funded by the Canada Foundation for Innovation under the auspices of Compute Canada; the Government of Ontario; Ontario Research Fund—Research Excellence; and the University of Toronto. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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N2 - © 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention at both the experimental and theoretical levels. Much of this work has been dedicated to bulk material studies, yet recent experimental work has shown the formation of highly efficient quantum-confined nanocrystals with tunable band edges. Here we investigate perovskite quantum dots from theory, predicting an upper bound of the Bohr radius of 45 Å that agrees well with literature values. When the quantum dots are stoichiometric, they are trap-free and have nearly symmetric contributions to confinement from the valence and conduction bands. We further show that surface-associated conduction bandedge states in perovskite nanocrystals lie below the bulk states, which could explain the difference in Urbach tails between mesoporous and planar perovskite films. In addition to conventional molecular dynamics (MD), we implement an enhanced phase-space sampling algorithm, replica exchange molecular dynamics (REMD). We find that in simulation of methylammonium orientation and global minima, REMD outperforms conventional MD. To the best of our knowledge, this is the first REMD implementation for realistic-sized systems in the realm of DFT calculations.

AB - © 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention at both the experimental and theoretical levels. Much of this work has been dedicated to bulk material studies, yet recent experimental work has shown the formation of highly efficient quantum-confined nanocrystals with tunable band edges. Here we investigate perovskite quantum dots from theory, predicting an upper bound of the Bohr radius of 45 Å that agrees well with literature values. When the quantum dots are stoichiometric, they are trap-free and have nearly symmetric contributions to confinement from the valence and conduction bands. We further show that surface-associated conduction bandedge states in perovskite nanocrystals lie below the bulk states, which could explain the difference in Urbach tails between mesoporous and planar perovskite films. In addition to conventional molecular dynamics (MD), we implement an enhanced phase-space sampling algorithm, replica exchange molecular dynamics (REMD). We find that in simulation of methylammonium orientation and global minima, REMD outperforms conventional MD. To the best of our knowledge, this is the first REMD implementation for realistic-sized systems in the realm of DFT calculations.

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DO - 10.1021/acs.jpcc.5b03613

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JO - The Journal of Physical Chemistry C

JF - The Journal of Physical Chemistry C

IS - 24

ER -

Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics

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