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Journal of Chemical Physics / Volume 132 / Issue 12 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 132, 124506 (2010); http://dx.doi.org/10.1063/1.3354108 (13 pages)

Structure and dynamics of the protic ionic liquid monomethylammonium nitrate ([CH3NH3][NO3]) from ab initio molecular dynamics simulations

Stefan Zahn, Jens Thar, and Barbara Kirchner

Wilhelm-Ostwald Institut für Physikalische und Theoretische Chemie, University of Leipzig, Linnéstraße. 2, D-04103, Leipzig, Germany

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(Received 7 October 2009; accepted 15 February 2010; published online 24 March 2010)

The dynamics of the protic ionic liquid monomethylammonium nitrate is investigated by Car–Parrinello molecular dynamics simulations. On average, 1.8 of 3 possible hydrogen bond contacts are formed. Therefore, one hydrogen bond acceptor and one donor site in each ion pair of monomethylammonium nitrate remains free, which is similar to water. Furthermore, like water, monomethylammonium nitrate exhibits a fast fluctuating hydrogen bond network. The comparable hydrogen bond network and dynamics of both liquids might explain the similar impact on reactivity and selectivity found for chemical reactions. However, the hydrogen bond network of monomethylammonium nitrate and water show some structural differences. While the hydrogen bonds in water arrange in parallel fashion, the hydrogen bonds of monomethylammonium nitrate prefer angles of 0°, 90°, and 180°. The ion dynamics of monomethylammonium nitrate indicate that at about 85% of the ion pairs are still connected after 14.5 ps. A closer inspection of the first solvation shell dynamics of one cation reveals that after 11 ps the current ion pair conformation is independent of the initial ion pair conformation because the ion pairs lose their information of the initial ion pair conformation much faster than the time needed to escape from their solvent cage. The ion dynamics of monomethylammonium nitrate can be described by the following model: There are ions rattling in long living cages which are formed by long living ion pairs.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. COMPUTATIONAL DETAILS
    1. MMAN
    2. Water
  3. RESULTS
    1. Liquid structure
      1. Structure directed by counterions
      2. Hydrogen bonds
      3. Structure directed by like ions
      4. Nanoscale segregation
    2. Ion pairing and ion dynamics
      1. Ion pair lifetimes depending on initial conformations
      2. Lifetime of a particular conformation
      3. Change in conformations
      4. Conformation memory loss of ion pairs
      5. Rotation of ions
    3. Hydrogen bond dynamics
  4. CONCLUSION

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KEYWORDS and PACS

Keywords

ab initio calculations, hydrogen bonds, liquid structure, molecular dynamics method, organic compounds

PACS

  • 71.15.-m

    Methods of electronic structure calculations

  • 61.50.Lt

    Crystal binding; cohesive energy

  • 61.25.-f

    Studies of specific liquid structures

  • 02.70.Ns

    Molecular dynamics and particle methods

  • 71.15.Pd

    Molecular dynamics calculations (Car-Parrinello) and other numerical simulations

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3354108

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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