# Thermal Effects on $CH_3NH_3PbI_3$ Perovskite from Ab Initio Molecular Dynamics Simulations

Carignano, Marcelo A; Kachmar, Ali; Hutter, Jürg (2015). Thermal Effects on $CH_3NH_3PbI_3$ Perovskite from Ab Initio Molecular Dynamics Simulations. Journal of Physical Chemistry C, 119(17):8991-8997.

## Abstract

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.

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.

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## Additional indexing

Item Type: Journal Article, refereed, original work 07 Faculty of Science > Department of Chemistry 540 Chemistry English 2015 21 Dec 2015 14:43 05 Apr 2016 19:30 American Chemical Society (ACS) 1932-7447 This document is the Accepted Manuscript version of a Published Work that appeared in final form in J Phys Chem, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jp510568n. https://doi.org/10.1021/jp510568n
Permanent URL: https://doi.org/10.5167/uzh-114309

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