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

Handle URI:
http://hdl.handle.net/10754/599169
Title:
Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics
Authors:
Buin, Andrei; Comin, Riccardo; Ip, Alexander H.; Sargent, Edward H.
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.
Citation:
Buin A, Comin R, Ip AH, Sargent EH (2015) Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics. The Journal of Physical Chemistry C 119: 13965–13971. Available: http://dx.doi.org/10.1021/acs.jpcc.5b03613.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
KAUST Grant Number:
KUS-11-009-21
Issue Date:
18-Jun-2015
DOI:
10.1021/acs.jpcc.5b03613
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
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.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorBuin, Andreien
dc.contributor.authorComin, Riccardoen
dc.contributor.authorIp, Alexander H.en
dc.contributor.authorSargent, Edward H.en
dc.date.accessioned2016-02-25T13:54:11Zen
dc.date.available2016-02-25T13:54:11Zen
dc.date.issued2015-06-18en
dc.identifier.citationBuin A, Comin R, Ip AH, Sargent EH (2015) Perovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamics. The Journal of Physical Chemistry C 119: 13965–13971. Available: http://dx.doi.org/10.1021/acs.jpcc.5b03613.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/acs.jpcc.5b03613en
dc.identifier.urihttp://hdl.handle.net/10754/599169en
dc.description.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.en
dc.description.sponsorshipThis 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titlePerovskite Quantum Dots Modeled Using ab Initio and Replica Exchange Molecular Dynamicsen
dc.typeArticleen
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.contributor.institutionUniversity of Toronto, Toronto, Canadaen
kaust.grant.numberKUS-11-009-21en
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