PMID- 29195043
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20180502
LR  - 20180502
IS  - 1520-5207 (Electronic)
IS  - 1520-5207 (Linking)
VI  - 122
IP  - 1
DP  - 2018 Jan 11
TI  - Grotthuss Transport of Iodide in EMIM/I(3) Ionic Crystal.
PG  - 250-257
LID - 10.1021/acs.jpcb.7b09292 [doi]
AB  - Highly ionic environments can mediate unusual chemical reactions that would 
      otherwise be considered impossible based on chemical intuition. For example, the 
      formation of a chemical bond between two iodide anions to form a divalent 
      polyiodide anion is seemingly prohibited due to Coulombic repulsion. Using ab 
      initio molecular dynamics simulations, we show that in the 
      1-ethyl-3-methylimidazolium (EMIM)/I(3) ionic crystal, the reactive formation of 
      divalent and even trivalent polyiodide anions occurs with extremely small 
      energetic barriers, due to the electrostatic field of the ionic lattice. A 
      practical consequence of this anomalous reactivity is that iodide anions are 
      efficiently transported within the crystal through a "Grotthuss-exchange" 
      mechanism involving bond-breaking and forming events. We characterize two 
      distinct transport pathways, involving both I(4)(2-) and I(7)(3-) intermediates, 
      with fast transport of iodide resulting from the release of an I(-) anion on the 
      opposite side of the intermediate species from the initial bond formation. The 
      ordered cation arrangement in the crystal provides the necessary electrostatic 
      screening for close approach of anions, suggesting a new counterintuitive 
      approach to obtain high ionic conductivity. This new design principle could be 
      used to develop better solid-state electrolytes for batteries, fuel cells, and 
      supercapacitors.
FAU - McDaniel, Jesse G
AU  - McDaniel JG
AUID- ORCID: 0000-0002-9211-1108
AD  - Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, 
      United States.
FAU - Yethiraj, Arun
AU  - Yethiraj A
AUID- ORCID: 0000-0002-8579-449X
AD  - Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, 
      United States.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
PT  - Research Support, U.S. Gov't, Non-P.H.S.
DEP - 20171222
PL  - United States
TA  - J Phys Chem B
JT  - The journal of physical chemistry. B
JID - 101157530
EDAT- 2017/12/02 06:00
MHDA- 2017/12/02 06:01
CRDT- 2017/12/02 06:00
PHST- 2017/12/02 06:00 [pubmed]
PHST- 2017/12/02 06:01 [medline]
PHST- 2017/12/02 06:00 [entrez]
AID - 10.1021/acs.jpcb.7b09292 [doi]
PST - ppublish
SO  - J Phys Chem B. 2018 Jan 11;122(1):250-257. doi: 10.1021/acs.jpcb.7b09292. Epub 
      2017 Dec 22.