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Title: Rotation mechanism of methylammonium molecules in organometal halide perovskite in cubic phase: An ab initio molecular dynamics study

Abstract

Rotation of methylammonium (CH3NH3 or MA) molecules is believed to govern the excellent transport properties of photocarriers in the MA lead iodide (MAPbI3) perovskite. Of particular interest is its cubic phase, which exists in industrially important films at room temperature. In order to investigate the rotational behaviors of the MA molecules, we have performed ab initio molecular dynamics simulations of cubic-MAPbI3 at room temperature. There are two types of rotational motions of MA molecules in a crystalline PbI3 cage: reorientation of a whole molecule and intramolecular rotation around the C–N bond within MA molecules. Using a cubic symmetry-assisted analysis (CSAA), we found that the prominent orientation of the C–N bond is the crystalline ❬110❭directions, rather than the ❬100❭ and ❬111❭ directions. Rapid rotation around the C–N bond is also observed, which easily occurs when the rotational axis is parallel to the ❬110❭ directions according to the CSAA. To explain the atomistic mechanisms underlying these CSAA results, we have focused on the relation between H–I hydrogen bonds and the orientation of an MA molecule. Here, the hydrogen bonds were defined by population analysis, and it has been found that, while H atoms in the CH3 group (HC) hardly interacts with Imore » atoms, those in the NH3 group (HN) form at least one hydrogen bond with I atoms and their interatomic distances are in a wide range, 2.2–3.7 Å. Based on these findings, we have given a possible explanation to why the ❬110❭ directions are preferred. Namely, the atomic arrangement and interatomic distance between MA and surrounding I atoms are most suitable for the formation of hydrogen bonds. In addition to films, these results are potentially applicable to the rotational behaviors in bulk MAPbI3 as well, considering that the atomistic structure and time constants regarding the rotation of MA molecules statistically agree with bulk experiments.« less

Authors:
ORCiD logo [1];  [2];  [2];  [3];  [3];  [3]
  1. Kobe Univ. (Japan)
  2. Kumamoto Univ. (Japan)
  3. Univ. of Southern California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1535291
Alternate Identifier(s):
OSTI ID: 1421232
Grant/Contract Number:  
FG02-04ER46130; # DE-FG02-04ER-46130
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Shimamura, Kohei, Hakamata, Tomoya, Shimojo, Fuyuki, Kalia, Rajiv K., Nakano, Aiichiro, and Vashishta, Priya. Rotation mechanism of methylammonium molecules in organometal halide perovskite in cubic phase: An ab initio molecular dynamics study. United States: N. p., 2016. Web. doi:10.1063/1.4971791.
Shimamura, Kohei, Hakamata, Tomoya, Shimojo, Fuyuki, Kalia, Rajiv K., Nakano, Aiichiro, & Vashishta, Priya. Rotation mechanism of methylammonium molecules in organometal halide perovskite in cubic phase: An ab initio molecular dynamics study. United States. doi:10.1063/1.4971791.
Shimamura, Kohei, Hakamata, Tomoya, Shimojo, Fuyuki, Kalia, Rajiv K., Nakano, Aiichiro, and Vashishta, Priya. Thu . "Rotation mechanism of methylammonium molecules in organometal halide perovskite in cubic phase: An ab initio molecular dynamics study". United States. doi:10.1063/1.4971791. https://www.osti.gov/servlets/purl/1535291.
@article{osti_1535291,
title = {Rotation mechanism of methylammonium molecules in organometal halide perovskite in cubic phase: An ab initio molecular dynamics study},
author = {Shimamura, Kohei and Hakamata, Tomoya and Shimojo, Fuyuki and Kalia, Rajiv K. and Nakano, Aiichiro and Vashishta, Priya},
abstractNote = {Rotation of methylammonium (CH3NH3 or MA) molecules is believed to govern the excellent transport properties of photocarriers in the MA lead iodide (MAPbI3) perovskite. Of particular interest is its cubic phase, which exists in industrially important films at room temperature. In order to investigate the rotational behaviors of the MA molecules, we have performed ab initio molecular dynamics simulations of cubic-MAPbI3 at room temperature. There are two types of rotational motions of MA molecules in a crystalline PbI3 cage: reorientation of a whole molecule and intramolecular rotation around the C–N bond within MA molecules. Using a cubic symmetry-assisted analysis (CSAA), we found that the prominent orientation of the C–N bond is the crystalline ❬110❭directions, rather than the ❬100❭ and ❬111❭ directions. Rapid rotation around the C–N bond is also observed, which easily occurs when the rotational axis is parallel to the ❬110❭ directions according to the CSAA. To explain the atomistic mechanisms underlying these CSAA results, we have focused on the relation between H–I hydrogen bonds and the orientation of an MA molecule. Here, the hydrogen bonds were defined by population analysis, and it has been found that, while H atoms in the CH3 group (HC) hardly interacts with I atoms, those in the NH3 group (HN) form at least one hydrogen bond with I atoms and their interatomic distances are in a wide range, 2.2–3.7 Å. Based on these findings, we have given a possible explanation to why the ❬110❭ directions are preferred. Namely, the atomic arrangement and interatomic distance between MA and surrounding I atoms are most suitable for the formation of hydrogen bonds. In addition to films, these results are potentially applicable to the rotational behaviors in bulk MAPbI3 as well, considering that the atomistic structure and time constants regarding the rotation of MA molecules statistically agree with bulk experiments.},
doi = {10.1063/1.4971791},
journal = {Journal of Chemical Physics},
number = 22,
volume = 145,
place = {United States},
year = {2016},
month = {12}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

The nature of free-carrier transport in organometal halide perovskites
journal, January 2016

  • Hakamata, Tomoya; Shimamura, Kohei; Shimojo, Fuyuki
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep19599

Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells
journal, August 2014

  • Frost, Jarvist M.; Butler, Keith T.; Walsh, Aron
  • APL Materials, Vol. 2, Issue 8
  • DOI: 10.1063/1.4890246

Band filling with free charge carriers in organometal halide perovskites
journal, August 2014


Projector augmented-wave method
journal, December 1994


Thermal Effects on CH 3 NH 3 PbI 3 Perovskite from Ab Initio Molecular Dynamics Simulations
journal, March 2015

  • Carignano, Marcelo A.; Kachmar, Ali; Hutter, Jürg
  • The Journal of Physical Chemistry C, Vol. 119, Issue 17
  • DOI: 10.1021/jp510568n

Population analysis of plane-wave electronic structure calculations of bulk materials
journal, December 1996


Temperature-Dependent Charge-Carrier Dynamics in CH 3 NH 3 PbI 3 Perovskite Thin Films
journal, September 2015

  • Milot, Rebecca L.; Eperon, Giles E.; Snaith, Henry J.
  • Advanced Functional Materials, Vol. 25, Issue 39
  • DOI: 10.1002/adfm.201502340

A crossover in anisotropic nanomechanochemistry of van der Waals crystals
journal, December 2015

  • Shimamura, Kohei; Misawa, Masaaki; Li, Ying
  • Applied Physics Letters, Vol. 107, Issue 23
  • DOI: 10.1063/1.4937268

A Broyden—Fletcher—Goldfarb—Shanno optimization procedure for molecular geometries
journal, December 1985


Microstructures and photovoltaic properties of perovskite-type CH 3 NH 3 PbI 3 compounds
journal, November 2014

  • Oku, Takeo; Zushi, Masahito; Imanishi, Yuma
  • Applied Physics Express, Vol. 7, Issue 12
  • DOI: 10.7567/APEX.7.121601

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics
journal, January 2015

  • Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 14
  • DOI: 10.1039/C5CP00599J

Structural and electronic properties of organo-halide lead perovskites: a combined IR-spectroscopy and ab initio molecular dynamics investigation
journal, January 2014

  • Mosconi, Edoardo; Quarti, Claudio; Ivanovska, Tanja
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 30
  • DOI: 10.1039/C4CP00569D

Structural Study on Cubic–Tetragonal Transition of CH 3 NH 3 PbI 3
journal, July 2002

  • Kawamura, Yukihiko; Mashiyama, Hiroyuki; Hasebe, Katsuhiko
  • Journal of the Physical Society of Japan, Vol. 71, Issue 7
  • DOI: 10.1143/JPSJ.71.1694

Reversible multiple time scale molecular dynamics
journal, August 1992

  • Tuckerman, M.; Berne, B. J.; Martyna, G. J.
  • The Journal of Chemical Physics, Vol. 97, Issue 3
  • DOI: 10.1063/1.463137

Electronic processes in fast thermite chemical reactions: A first-principles molecular dynamics study
journal, June 2008


Screening in crystalline liquids protects energetic carriers in hybrid perovskites
journal, September 2016


Hydrogen-on-Demand Using Metallic Alloy Nanoparticles in Water
journal, June 2014

  • Shimamura, Kohei; Shimojo, Fuyuki; Kalia, Rajiv K.
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl501612v

Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
journal, April 2014

  • Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500390f

Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015


First-Principles Study of Lead Iodide Perovskite Tetragonal and Orthorhombic Phases for Photovoltaics
journal, August 2014

  • Geng, Wei; Zhang, Le; Zhang, Yan-Ning
  • The Journal of Physical Chemistry C, Vol. 118, Issue 34
  • DOI: 10.1021/jp504951h

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013

  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

Slow Dynamic Processes in Lead Halide Perovskite Solar Cells. Characteristic Times and Hysteresis
journal, June 2014

  • Sanchez, Rafael S.; Gonzalez-Pedro, Victoria; Lee, Jin-Wook
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz5011187

Halide perovskite materials for solar cells: a theoretical review
journal, January 2015

  • Yin, Wan-Jian; Yang, Ji-Hui; Kang, Joongoo
  • Journal of Materials Chemistry A, Vol. 3, Issue 17
  • DOI: 10.1039/C4TA05033A

Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I
journal, October 1955

  • Mulliken, R. S.
  • The Journal of Chemical Physics, Vol. 23, Issue 10
  • DOI: 10.1063/1.1740588

First-Principles Modeling of Mixed Halide Organometal Perovskites for Photovoltaic Applications
journal, July 2013

  • Mosconi, Edoardo; Amat, Anna; Nazeeruddin, Md. K.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 27
  • DOI: 10.1021/jp4048659

Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K
journal, January 2015

  • Weller, Mark T.; Weber, Oliver J.; Henry, Paul F.
  • Chemical Communications, Vol. 51, Issue 20
  • DOI: 10.1039/C4CC09944C

The Raman Spectrum of the CH 3 NH 3 PbI 3 Hybrid Perovskite: Interplay of Theory and Experiment
journal, December 2013

  • Quarti, Claudio; Grancini, Giulia; Mosconi, Edoardo
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 2
  • DOI: 10.1021/jz402589q

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Fabrication and Characterization of TiO 2 /CH 3 NH 3 PbI 3 -based Photovoltaic Devices
journal, June 2014

  • Zushi, Masahito; Suzuki, Atsushi; Akiyama, Tsuyoshi
  • Chemistry Letters, Vol. 43, Issue 6
  • DOI: 10.1246/cl.140127

A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984


Photocarrier Recombination Dynamics in Perovskite CH 3 NH 3 PbI 3 for Solar Cell Applications
journal, August 2014

  • Yamada, Yasuhiro; Nakamura, Toru; Endo, Masaru
  • Journal of the American Chemical Society, Vol. 136, Issue 33
  • DOI: 10.1021/ja506624n

Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy
journal, December 1987

  • Poglitsch, A.; Weber, D.
  • The Journal of Chemical Physics, Vol. 87, Issue 11, p. 6373-6378
  • DOI: 10.1063/1.453467

Hybrid perovskites for photovoltaics: Insights from first principles
journal, March 2014


Unusual defect physics in CH 3 NH 3 PbI 3 perovskite solar cell absorber
journal, February 2014

  • Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa
  • Applied Physics Letters, Vol. 104, Issue 6
  • DOI: 10.1063/1.4864778

Cation rotation in methylammonium lead halides
journal, November 1985


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Inhomogeneous Electron Gas
journal, November 1964


Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013

  • Stranks, S. D.; Eperon, G. E.; Grancini, G.
  • Science, Vol. 342, Issue 6156, p. 341-344
  • DOI: 10.1126/science.1243982

Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells
journal, May 2015

  • Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8124

How hybrid perovskites get their groove
journal, September 2016


The classification of tilted octahedra in perovskites
journal, November 1972

  • Glazer, A. M.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 11
  • DOI: 10.1107/S0567740872007976

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985


The Anti-Polar Structure of CH3NH3PbBr3
journal, August 2007

  • Mashiyama, H.; Kawamura, Y.; Kubota, Y.
  • Journal of the Korean Physical Society, Vol. 51, Issue 92
  • DOI: 10.3938/jkps.51.850

Analysis of atomic orbital basis sets from the projection of plane-wave results
journal, May 1996

  • Sánchez-Portal, Daniel; Artacho, Emilio; Soler, José M.
  • Journal of Physics: Condensed Matter, Vol. 8, Issue 21
  • DOI: 10.1088/0953-8984/8/21/012

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Perovskite solar cells: an emerging photovoltaic technology
journal, March 2015


Perovskite Solar Cells: From Materials to Devices
journal, October 2014


Molecular disorder and translation/rotation coupling in the plastic crystal phase of hybrid perovskites
journal, January 2016


Structural and electronic properties of hybrid perovskites for high-efficiency thin-film photovoltaics from first-principles
journal, October 2013

  • Brivio, Federico; Walker, Alison B.; Walsh, Aron
  • APL Materials, Vol. 1, Issue 4
  • DOI: 10.1063/1.4824147

Alkylammonium lead halides. Part 2. CH 3 NH 3 PbX 3 (X = Cl, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation
journal, March 1990

  • Knop, Osvald; Wasylishen, Roderick E.; White, Mary Anne
  • Canadian Journal of Chemistry, Vol. 68, Issue 3
  • DOI: 10.1139/v90-063

Pedestrian Guide to Symmetry Properties of the Reference Cubic Structure of 3D All-Inorganic and Hybrid Perovskites
journal, June 2015


Structure of Methylammonium Lead Iodide Within Mesoporous Titanium Dioxide: Active Material in High-Performance Perovskite Solar Cells
journal, December 2013

  • Choi, Joshua J.; Yang, Xiaohao; Norman, Zachariah M.
  • Nano Letters, Vol. 14, Issue 1, p. 127-133
  • DOI: 10.1021/nl403514x

Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells
journal, June 2014

  • Juarez-Perez, Emilio J.; Sanchez, Rafael S.; Badia, Laura
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz5011169

Linear-scaling density-functional-theory calculations of electronic structure based on real-space grids: design, analysis, and scalability test of parallel algorithms
journal, November 2001


Barmer to internal rotation in the methylammonium ion
journal, November 1975


Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites
journal, August 2015

  • Bakulin, Artem A.; Selig, Oleg; Bakker, Huib J.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
  • DOI: 10.1021/acs.jpclett.5b01555

Inhomogeneous Electron Gas
journal, March 1973


    Works referencing / citing this record:

    Dynamic Disorder Restriction of Methylammonium (MA) Groups in Chloride‐Doped MAPbBr 3 Hybrid Perovskites: A Neutron Powder Diffraction Study
    journal, March 2019

    • López, Carlos Alberto; Álvarez‐Galván, María Consuelo; Martínez‐Huerta, María Victoria
    • Chemistry – A European Journal, Vol. 25, Issue 17
    • DOI: 10.1002/chem.201806246

    Dynamic Disorder Restriction of Methylammonium (MA) Groups in Chloride‐Doped MAPbBr 3 Hybrid Perovskites: A Neutron Powder Diffraction Study
    journal, March 2019

    • López, Carlos Alberto; Álvarez‐Galván, María Consuelo; Martínez‐Huerta, María Victoria
    • Chemistry – A European Journal, Vol. 25, Issue 17
    • DOI: 10.1002/chem.201806246