### Abstract

We present a molecular dynamics simulation study of CH<inf>3</inf>NH<inf>3</inf>PbI<inf>3</inf> based on forces calculated from density functional theory. The simulations were performed on model systems having 8 and 27 unit cells, and for a total simulation time of 40 ps in each case. Analysis of the finite size effects, in particular the mobility of the organic component, suggests that the smaller system is over-correlated through the long-range electrostatic interaction. In the larger system, this finite size artifact is relaxed, producing a more reliable description of the anisotropic rotational behavior of the methylammonium molecules. The thermal effects on the optical properties of the system were also analyzed. The HOMO-LUMO energy gap fluctuates around its central value with a standard deviation of approximately 0.1 eV. The projected density of states consistently place the Fermi level on the p orbitals of the I atoms and the lowest virtual state on the p orbitals of the Pb atoms throughout the whole simulation trajectory.

Original language | English |
---|---|

Pages (from-to) | 8991-8997 |

Number of pages | 7 |

Journal | Journal of Physical Chemistry C |

Volume | 119 |

Issue number | 17 |

DOIs | |

Publication status | Published - 30 Apr 2015 |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry
- Electronic, Optical and Magnetic Materials
- Surfaces, Coatings and Films
- Energy(all)

### Cite this

**Thermal effects on CH<inf>3</inf>NH<inf>3</inf>PbI<inf>3</inf> perovskite from Ab initio molecular dynamics simulations.** / Carignano, Marcelo; Kachmar, Ali; Hutter, Jürg.

Research output: Contribution to journal › Article

*Journal of Physical Chemistry C*, vol. 119, no. 17, pp. 8991-8997. https://doi.org/10.1021/jp510568n

}

TY - JOUR

T1 - Thermal effects on CH3NH3PbI3 perovskite from Ab initio molecular dynamics simulations

AU - Carignano, Marcelo

AU - Kachmar, Ali

AU - Hutter, Jürg

PY - 2015/4/30

Y1 - 2015/4/30

N2 - We present a molecular dynamics simulation study of CH3NH3PbI3 based on forces calculated from density functional theory. The simulations were performed on model systems having 8 and 27 unit cells, and for a total simulation time of 40 ps in each case. Analysis of the finite size effects, in particular the mobility of the organic component, suggests that the smaller system is over-correlated through the long-range electrostatic interaction. In the larger system, this finite size artifact is relaxed, producing a more reliable description of the anisotropic rotational behavior of the methylammonium molecules. The thermal effects on the optical properties of the system were also analyzed. The HOMO-LUMO energy gap fluctuates around its central value with a standard deviation of approximately 0.1 eV. The projected density of states consistently place the Fermi level on the p orbitals of the I atoms and the lowest virtual state on the p orbitals of the Pb atoms throughout the whole simulation trajectory.

AB - We present a molecular dynamics simulation study of CH3NH3PbI3 based on forces calculated from density functional theory. The simulations were performed on model systems having 8 and 27 unit cells, and for a total simulation time of 40 ps in each case. Analysis of the finite size effects, in particular the mobility of the organic component, suggests that the smaller system is over-correlated through the long-range electrostatic interaction. In the larger system, this finite size artifact is relaxed, producing a more reliable description of the anisotropic rotational behavior of the methylammonium molecules. The thermal effects on the optical properties of the system were also analyzed. The HOMO-LUMO energy gap fluctuates around its central value with a standard deviation of approximately 0.1 eV. The projected density of states consistently place the Fermi level on the p orbitals of the I atoms and the lowest virtual state on the p orbitals of the Pb atoms throughout the whole simulation trajectory.

UR - http://www.scopus.com/inward/record.url?scp=84928889754&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84928889754&partnerID=8YFLogxK

U2 - 10.1021/jp510568n

DO - 10.1021/jp510568n

M3 - Article

AN - SCOPUS:84928889754

VL - 119

SP - 8991

EP - 8997

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 17

ER -