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Hybrid organic–inorganic CH 3 NH 3 PbI 3 perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design
Author(s) -
Varadwaj Arpita,
Varadwaj Pradeep R.,
Yamashita Koichi
Publication year - 2017
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25073
Subject(s) - mulliken population analysis , intermolecular force , perovskite (structure) , density functional theory , hydrogen bond , chemical physics , chemistry , band gap , van der waals force , binding energy , materials science , computational chemistry , crystallography , molecule , physics , atomic physics , optoelectronics , organic chemistry
Methylammonium lead iodide (CH 3 NH 3 PbI 3 ) perovskite compound has produced a remarkable breakthrough in the photovoltaic history of solar cell technology because of its outstanding device‐based performance as a light‐harvesting semiconductor. Whereas the experimental and theoretical studies of this system in the solid state have been numerously reported in the last 4 years, its fundamental cluster physics is yet to be exploited. To this end, this study has performed theoretical investigations using DFT‐M06‐2X/ADZP to examine the principal geometrical, electronic, topological, and orbital properties of the CH 3 NH 3 PbI 3 molecular building block. The intermolecular hydrogen bonded interactions examined for the most important conformers of the system are found to be unusually strong, with binding energies lying between −93.53 and −125.11 kcal mol −1 (beyond the covalent limit, −40 kcal mol −1 ), enabling us to classify the underlying interactions as ultra‐strong type since their characteristic properties are unidentical with those have already been proposed as very strong, strong, moderate, weak, and van der Waals. Based on this, together with the unusually high charge transfers, strong hyperconjugative interactions, sophisticated topologies of the charge density, and short intermolecular distances of separation, we have characterized the conformers of CH 3 NH 3 PbI 3 as Mulliken inner complexes. The consequences of these, as well as of the ultra‐strong interactions, in designing novel functional nanomaterials are outlined. © 2017 Wiley Periodicals, Inc.