The molecular structures and the relationships between the calculated molecular and observed bulk phase properties of phosphonium-based ionic liquids

Ryan P. Morco, Ahmed Y. Musa, J. Clara Wren

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The molecular and electronic structures of six ionic liquids (ILs) having the same cation (tetradecyl(trihexyl)phosphonium [P66614]), but with different anions, were obtained by quantum chemical calculations using density functional theory (DFT). Various molecular parameters were computed, including the inter-ionic H-bond length and angle, the energies of various molecular orbitals including HOMO and LUMO, the dipole moment (μ), the cation-anion interaction energy (†E) and the electrostatic potential. The wavelengths and oscillator strengths of vibrational and electronic transition lines were also calculated and found to be in good agreement with measured IR and UV-vis absorption spectra. We have found strong correlations between the calculated quantum chemical parameters and the measured physical and chemical properties of the phosphonium ILs. In general, molar conductivity (Λ) increases, whereas viscosity decreases, exponentially with μ, and the melting point increases linearly with - †E.

Original languageEnglish
Pages (from-to)74-81
Number of pages8
JournalSolid State Ionics
Volume258
DOIs
Publication statusPublished - 1 May 2014
Externally publishedYes

Fingerprint

Ionic Liquids
Ionic liquids
Molecular structure
Anions
Cations
molecular structure
Negative ions
Positive ions
anions
cations
Dipole moment
Bond length
Molecular orbitals
liquids
chemical properties
oscillator strengths
Chemical properties
Electronic structure
melting points
Density functional theory

Keywords

  • Electronic transitions
  • Electrostatic potential
  • Phosphonium ionic liquids
  • Quantum chemical calculations
  • Vibrational frequencies

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Chemistry(all)

Cite this

The molecular structures and the relationships between the calculated molecular and observed bulk phase properties of phosphonium-based ionic liquids. / Morco, Ryan P.; Musa, Ahmed Y.; Clara Wren, J.

In: Solid State Ionics, Vol. 258, 01.05.2014, p. 74-81.

Research output: Contribution to journalArticle

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