Abstract
In this article we determine the temperature-dependent structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid using a combination of X-ray scattering and molecular dynamics simulations. As in many other room-temperature ionic liquids three characteristic intermolecular peaks can be detected in the structure function S(q). A prepeak or first sharp diffraction peak is observed at about q = 0.42 Å -1. Long range anion-anion correlations are the most important contributors to this peak. In all systems we have studied to date, this prepeak is a signature of solvation asymmetry. The peak in S(q) near q = 0.75 Å -1 is the signature of ionic alternation and arises from the charge ordered separation of ions of the same charge. The most intense diffraction peak near q = 1.37 Å -1 arises from short-range separation between ions of opposite charge combined with a significant contribution from cationic carbon-carbon interactions, indicating that cationic hydrophobic tails have significant contacts.
| Original language | English |
|---|---|
| Pages (from-to) | 133-143 |
| Number of pages | 11 |
| Journal | Faraday Discussions |
| Volume | 154 |
| DOIs | |
| Publication status | Published - 2012 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Temperature-dependent structure of ionic liquids : X-ray scattering and simulations. / Kashyap, Hemant K.; Santos, Cherry S.; Annapureddy, Harsha V R; Murthy, N. Sanjeeva; Margulis, Claudio J.; Castner, Ed.
In: Faraday Discussions, Vol. 154, 2012, p. 133-143.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Temperature-dependent structure of ionic liquids
T2 - X-ray scattering and simulations
AU - Kashyap, Hemant K.
AU - Santos, Cherry S.
AU - Annapureddy, Harsha V R
AU - Murthy, N. Sanjeeva
AU - Margulis, Claudio J.
AU - Castner, Ed
PY - 2012
Y1 - 2012
N2 - In this article we determine the temperature-dependent structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid using a combination of X-ray scattering and molecular dynamics simulations. As in many other room-temperature ionic liquids three characteristic intermolecular peaks can be detected in the structure function S(q). A prepeak or first sharp diffraction peak is observed at about q = 0.42 Å -1. Long range anion-anion correlations are the most important contributors to this peak. In all systems we have studied to date, this prepeak is a signature of solvation asymmetry. The peak in S(q) near q = 0.75 Å -1 is the signature of ionic alternation and arises from the charge ordered separation of ions of the same charge. The most intense diffraction peak near q = 1.37 Å -1 arises from short-range separation between ions of opposite charge combined with a significant contribution from cationic carbon-carbon interactions, indicating that cationic hydrophobic tails have significant contacts.
AB - In this article we determine the temperature-dependent structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid using a combination of X-ray scattering and molecular dynamics simulations. As in many other room-temperature ionic liquids three characteristic intermolecular peaks can be detected in the structure function S(q). A prepeak or first sharp diffraction peak is observed at about q = 0.42 Å -1. Long range anion-anion correlations are the most important contributors to this peak. In all systems we have studied to date, this prepeak is a signature of solvation asymmetry. The peak in S(q) near q = 0.75 Å -1 is the signature of ionic alternation and arises from the charge ordered separation of ions of the same charge. The most intense diffraction peak near q = 1.37 Å -1 arises from short-range separation between ions of opposite charge combined with a significant contribution from cationic carbon-carbon interactions, indicating that cationic hydrophobic tails have significant contacts.
UR - http://www.scopus.com/inward/record.url?scp=82455174367&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=82455174367&partnerID=8YFLogxK
U2 - 10.1039/c1fd00059d
DO - 10.1039/c1fd00059d
M3 - Article
C2 - 22455018
AN - SCOPUS:82455174367
VL - 154
SP - 133
EP - 143
JO - Faraday Discussions
JF - Faraday Discussions
SN - 1364-5498
ER -