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Cohesive Properties of Ionic Liquids Calculated from First Principles

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F19%3A43918063" target="_blank" >RIV/60461373:22340/19:43918063 - isvavai.cz</a>

  • Result on the web

    <a href="https://doi.org/10.1021/acs.jctc.9b00625" target="_blank" >https://doi.org/10.1021/acs.jctc.9b00625</a>

  • DOI - Digital Object Identifier

    <a href="http://dx.doi.org/10.1021/acs.jctc.9b00625" target="_blank" >10.1021/acs.jctc.9b00625</a>

Alternative languages

  • Result language

    angličtina

  • Original language name

    Cohesive Properties of Ionic Liquids Calculated from First Principles

  • Original language description

    Low volatility of ionic liquids (ILs), being one of their most valuable properties, is also the principal factor making reliable measurements of vapor pressures and vaporization (or sublimation) enthalpies of ILs extremely difficult. Alternatively, vaporization enthalpies at the temperature of the triple point can be obtained from the enthalpies of sublimation and fusion. While the latter can be obtained calorimetrically with a fair accuracy, the former is in principle accessible through ab initio computations. This work assesses the performance of the first-principles calculations of sublimation properties of ILs. Namely, 3 compounds, coupling the 1-ethyl-3-methylimidazolium cation [emIm] with either tetrafluoroborate [BF4], hexafluorophosphate [PF6], or bis(trifluoromethylsulfonyl)imide [NTf2] anions were selected for a case study. A computational methodology, originally developed for molecular crystals, is adopted for crystals of ILs. It exploits periodic density functional theory (DFT) calculations of the unit-cell geometries and quasi-harmonic phonons and many-body expansion schemes for ab initio refinements of the lattice energies of crystalline ILs. The vapor phase is treated as the ideal gas whose properties are obtained combining the rigid rotor-harmonic oscillator model with corrections from the one-dimensional hindered rotors and molecular-dynamics simulations capturing the contributions from the interionic interaction modes. Although the given computational approach enables one to reach the chemical accuracy (4 kJ mol-1) of calculated sublimation enthalpies of simple molecular crystals, reaching the same level of accuracy for ionic liquids proves challenging as crystals of ionic liquids are bound appreciably stronger than common molecular crystals, the underlying cohesive energies of solid ionic liquids is up to 1 order of magnitude larger. Still, combination of the mentioned computational and experimental frameworks results in a novel promising scheme that is expected to generate reliable and accurate temperature-dependent data on sublimation (and vaporization) of ILs. Copyright © 2019 American Chemical Society.

  • Czech name

  • Czech description

Classification

  • Type

    J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database

  • CEP classification

  • OECD FORD branch

    10403 - Physical chemistry

Result continuities

  • Project

    <a href="/en/project/GJ19-04150Y" target="_blank" >GJ19-04150Y: Cohesive properties and phase equilibria of ionic liquids investigated by state of the art calculations and experiments</a><br>

  • Continuities

    P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Others

  • Publication year

    2019

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    Journal of Chemical Theory and Computation

  • ISSN

    1549-9618

  • e-ISSN

  • Volume of the periodical

    15

  • Issue of the periodical within the volume

    10

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    16

  • Pages from-to

    5563-5578

  • UT code for WoS article

    000489678700034

  • EID of the result in the Scopus database

    2-s2.0-85072639527