skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

Rotation of methylammonium (CH 3NH 3 or MA) molecules is believed to govern the excellent transport properties of photocarriers in the MA lead iodide (MAPbI 3) 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-MAPbI 3 at room temperature. There are two types of rotational motions of MA molecules in a crystalline PbI 3 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 CHmore » 3 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 MAPbI 3 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) (SC-22)
OSTI Identifier:
1535291
Alternate Identifier(s):
OSTI ID: 1421232
Grant/Contract Number:  
FG02-04ER46130; # DE-FG02-04ER-46130
Resource Type:
Journal Article: 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},
issn = {0021-9606},
number = 22,
volume = 145,
place = {United States},
year = {2016},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

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

Projector augmented-wave method
journal, December 1994


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


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

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


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

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


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

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