Structure of cyano-anion ionic liquids: X-ray scattering and simulations

Kamal B. Dhungana, Luiz F O Faria, Boning Wu, Min Liang, Mauro C C Ribeiro, Claudio J. Margulis, Ed Castner

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN-, SCN-, N(CN)2-, C(CN)3-, and B(CN)4-. By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4- anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1+/B(CN)4- is cationic.

Original languageEnglish
Article number024503
JournalJournal of Chemical Physics
Volume145
Issue number2
DOIs
Publication statusPublished - Jul 14 2016

Fingerprint

Ionic Liquids
X ray scattering
Anions
anions
liquids
scattering
x rays
simulation
Excited states
Discrete Fourier transforms
Melting point
Molecular dynamics
Cations
Boundary conditions
polarity
Viscosity
melting
viscosity
boundary conditions
molecular dynamics

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Dhungana, K. B., Faria, L. F. O., Wu, B., Liang, M., Ribeiro, M. C. C., Margulis, C. J., & Castner, E. (2016). Structure of cyano-anion ionic liquids: X-ray scattering and simulations. Journal of Chemical Physics, 145(2), [024503]. https://doi.org/10.1063/1.4955186

Structure of cyano-anion ionic liquids : X-ray scattering and simulations. / Dhungana, Kamal B.; Faria, Luiz F O; Wu, Boning; Liang, Min; Ribeiro, Mauro C C; Margulis, Claudio J.; Castner, Ed.

In: Journal of Chemical Physics, Vol. 145, No. 2, 024503, 14.07.2016.

Research output: Contribution to journalArticle

Dhungana, KB, Faria, LFO, Wu, B, Liang, M, Ribeiro, MCC, Margulis, CJ & Castner, E 2016, 'Structure of cyano-anion ionic liquids: X-ray scattering and simulations', Journal of Chemical Physics, vol. 145, no. 2, 024503. https://doi.org/10.1063/1.4955186
Dhungana KB, Faria LFO, Wu B, Liang M, Ribeiro MCC, Margulis CJ et al. Structure of cyano-anion ionic liquids: X-ray scattering and simulations. Journal of Chemical Physics. 2016 Jul 14;145(2). 024503. https://doi.org/10.1063/1.4955186
Dhungana, Kamal B. ; Faria, Luiz F O ; Wu, Boning ; Liang, Min ; Ribeiro, Mauro C C ; Margulis, Claudio J. ; Castner, Ed. / Structure of cyano-anion ionic liquids : X-ray scattering and simulations. In: Journal of Chemical Physics. 2016 ; Vol. 145, No. 2.
@article{02e5df800d4d48c0bb53e0b0f53f1f49,
title = "Structure of cyano-anion ionic liquids: X-ray scattering and simulations",
abstract = "Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN-, SCN-, N(CN)2-, C(CN)3-, and B(CN)4-. By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4- anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1+/B(CN)4- is cationic.",
author = "Dhungana, {Kamal B.} and Faria, {Luiz F O} and Boning Wu and Min Liang and Ribeiro, {Mauro C C} and Margulis, {Claudio J.} and Ed Castner",
year = "2016",
month = "7",
day = "14",
doi = "10.1063/1.4955186",
language = "English",
volume = "145",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "2",

}

TY - JOUR

T1 - Structure of cyano-anion ionic liquids

T2 - X-ray scattering and simulations

AU - Dhungana, Kamal B.

AU - Faria, Luiz F O

AU - Wu, Boning

AU - Liang, Min

AU - Ribeiro, Mauro C C

AU - Margulis, Claudio J.

AU - Castner, Ed

PY - 2016/7/14

Y1 - 2016/7/14

N2 - Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN-, SCN-, N(CN)2-, C(CN)3-, and B(CN)4-. By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4- anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1+/B(CN)4- is cationic.

AB - Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN-, SCN-, N(CN)2-, C(CN)3-, and B(CN)4-. By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4- anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1+/B(CN)4- is cationic.

UR - http://www.scopus.com/inward/record.url?scp=84978698181&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84978698181&partnerID=8YFLogxK

U2 - 10.1063/1.4955186

DO - 10.1063/1.4955186

M3 - Article

AN - SCOPUS:84978698181

VL - 145

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 2

M1 - 024503

ER -