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Title: Proton Hopping Mechanisms in a Protic Organic Ionic Plastic Crystal
Authors: Mondal, Anirban
Balasubramanian, Sundaram
Keywords: Chemistry
Materials Science
Space Gaussian Pseudopotentials
Solid-State Nmr
Phosphonic Acid
Intermediate Temperature
Canonical Ensemble
Protogenic Group
Issue Date: 2016
Publisher: American Chemical Society
Citation: Mondal, A.; Balasubramanian, S., Proton Hopping Mechanisms in a Protic Organic Ionic Plastic Crystal. Journal of Physical Chemistry C 2016, 120 (40), 22903-22909
Journal of Physical Chemistry C
Abstract: We elucidate the dynamics and mechanism of proton transport in a protic organic ionic plastic crystal (POIPC) [TAZ][pfBu] by means of BornOppenheimer molecular dynamics simulations at 400 K and zero humidity. The arrangement of ionic species in the crystal offers a two-dimensional hydrogen bond network along which an acidic proton can travel from one cation to another through a sequence of molecular reorientations. The results suggest spontaneous autodissociation of the NHN bond in the cation and multiple proton shuttle events from the cations nitrogen to the anions oxygen site in a native crystal. A complete proton transfer event is observed in simulations of a defective crystal with a single proton hole created in the cation. The barrier for proton transfer is determined using ab initio metadynamics simulations to be 7 kcal/mol, in agreement with experimental conductivity data. Using gas phase quantum chemical calculations, we propose [TAZ][CF3CF2CH2CF2SO3] as a compound that can show enhanced conductivity compared to that of [TAZ][pfBu].
Description: Restricted Access
ISSN: 1932-7447
Appears in Collections:Research Articles (Balasubramanian Sundaram)

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