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Title: Odd–even structural sensitivity on dynamics in network-forming ionic liquids

Abstract

Understanding structural sensitivity on properties of materials is an important step toward the rational design of materials. As a compelling case of sensitive structure-property relationship, an odd-even effect refers to the alternating trend of physical or chemical properties on odd/even number of repeating structural units. In crystalline or semi-crystalline materials, such odd-even variations of macroscopic properties emerge as manifestations of differences in the periodic packing patterns of molecules. Therefore, due to the lack of long-range order, such odd-even phenomenon is not expected in liquids. Herein, we report the discovery of a remarkable odd-even effect of the dynamical properties in the liquid phase, which challenges the traditional periodic packing explanations. In a class of network-forming ionic liquid (NIL), using incoherent quasi-elastic neutron scattering measurements, we measured the dynamical properties including the diffusion coefficient and the rotational relaxation time. These dynamical properties showed pronounced alternating trends with increased number of methylene (–CH2– ) groups in the backbone. Meanwhile, the structure factor S(Q) showed no long-range periodic packing of molecules, while the pair distribution function g(r) revealed subtle differences in the local molecular morphology. As a result, the observed dynamical odd-even phenomenon in liquids showed that profound dynamical changes originate from subtle localmore » structural differences.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [1];  [1]
  1. Univ. of Illinois, Urbana-Champaign, Urbana, IL (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1334425
Grant/Contract Number:  
AC05-00OR22725; SC-0014804; DMR-1508249
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 9; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Yang, Ke, Cai, Zhikun, Tyagi, Madhusudan, Feygenson, Mikhail, Neuefeind, Joerg C., Moore, Jeffrey S., and Zhang, Yang. Odd–even structural sensitivity on dynamics in network-forming ionic liquids. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b01429.
Yang, Ke, Cai, Zhikun, Tyagi, Madhusudan, Feygenson, Mikhail, Neuefeind, Joerg C., Moore, Jeffrey S., & Zhang, Yang. Odd–even structural sensitivity on dynamics in network-forming ionic liquids. United States. doi:10.1021/acs.chemmater.6b01429.
Yang, Ke, Cai, Zhikun, Tyagi, Madhusudan, Feygenson, Mikhail, Neuefeind, Joerg C., Moore, Jeffrey S., and Zhang, Yang. Wed . "Odd–even structural sensitivity on dynamics in network-forming ionic liquids". United States. doi:10.1021/acs.chemmater.6b01429. https://www.osti.gov/servlets/purl/1334425.
@article{osti_1334425,
title = {Odd–even structural sensitivity on dynamics in network-forming ionic liquids},
author = {Yang, Ke and Cai, Zhikun and Tyagi, Madhusudan and Feygenson, Mikhail and Neuefeind, Joerg C. and Moore, Jeffrey S. and Zhang, Yang},
abstractNote = {Understanding structural sensitivity on properties of materials is an important step toward the rational design of materials. As a compelling case of sensitive structure-property relationship, an odd-even effect refers to the alternating trend of physical or chemical properties on odd/even number of repeating structural units. In crystalline or semi-crystalline materials, such odd-even variations of macroscopic properties emerge as manifestations of differences in the periodic packing patterns of molecules. Therefore, due to the lack of long-range order, such odd-even phenomenon is not expected in liquids. Herein, we report the discovery of a remarkable odd-even effect of the dynamical properties in the liquid phase, which challenges the traditional periodic packing explanations. In a class of network-forming ionic liquid (NIL), using incoherent quasi-elastic neutron scattering measurements, we measured the dynamical properties including the diffusion coefficient and the rotational relaxation time. These dynamical properties showed pronounced alternating trends with increased number of methylene (–CH2– ) groups in the backbone. Meanwhile, the structure factor S(Q) showed no long-range periodic packing of molecules, while the pair distribution function g(r) revealed subtle differences in the local molecular morphology. As a result, the observed dynamical odd-even phenomenon in liquids showed that profound dynamical changes originate from subtle local structural differences.},
doi = {10.1021/acs.chemmater.6b01429},
journal = {Chemistry of Materials},
number = 9,
volume = 28,
place = {United States},
year = {2016},
month = {4}
}

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Works referencing / citing this record:

Anomalous and Not-So-Common Behavior in Common Ionic Liquids and Ionic Liquid-Containing Systems
journal, June 2019

  • Esperança, José M. S. S.; Tariq, Mohammad; Pereiro, Ana B.
  • Frontiers in Chemistry, Vol. 7
  • DOI: 10.3389/fchem.2019.00450

Anomalous and Not-So-Common Behavior in Common Ionic Liquids and Ionic Liquid-Containing Systems
journal, June 2019

  • Esperança, José M. S. S.; Tariq, Mohammad; Pereiro, Ana B.
  • Frontiers in Chemistry, Vol. 7
  • DOI: 10.3389/fchem.2019.00450