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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Effect of alkyl-group flexibility on the melting point of imidazolium-based ionic liquids

Full text
Author(s):
Bernardino, Kalil [1] ; Zhang, Yong [2] ; Ribeiro, Mauro C. C. [1] ; Maginn, Edward J. [2]
Total Authors: 4
Affiliation:
[1] Univ Sao Paulo, Dept Quim Fundamental, Inst Quim, Lab Espectroscopia Mol, Av Prof Lineu Prestes 748, BR-05508000 Sao Paulo - Brazil
[2] Univ Notre Dame, Dept Chem & Biomol Engn, Notre Dame, IN 46556 - USA
Total Affiliations: 2
Document type: Journal article
Source: Journal of Chemical Physics; v. 153, n. 4 JUL 28 2020.
Web of Science Citations: 0
Abstract

The low melting point of room temperature ionic liquids is usually explained in terms of the presence of bulky, low-symmetry, and flexible ions, with the first two factors related to the lattice energy while an entropic effect is attributed to the latter. By means of molecular dynamics simulations, the melting points of 1-ethyl-3-methyl-imidazolium hexafluorophosphate and 1-decyl-3-methyl-imidazolium hexafluorophosphate were determined, and the effect of the molecular flexibility over the melting point was explicitly computed by restraining the rotation of dihedral angles in both the solid and the liquid phases. The rotational flexibility over the bond between the ring and the alkyl chain affects the relative ordering of the anions around the cations and results in substantial effects over both the enthalpy and the entropy of melting. For the other dihedral angles of the alkyl group, the contributions are predominantly entropic and an alternating behavior was found. The flexibility of some dihedral angles has negligible effects on the melting point, while others can lead to differences in the melting point as large as 20 K. This alternating behavior is rationalized by the different probabilities of conformation defects in the crystal. (AU)

FAPESP's process: 16/21070-5 - Vibrational spectroscopy with spatial resolution
Grantee:Mauro Carlos Costa Ribeiro
Support Opportunities: Research Projects - Thematic Grants
FAPESP's process: 17/12063-8 - Non-equilibrium molecular dynamics of ionic liquids
Grantee:Kalil Bernardino
Support Opportunities: Scholarships in Brazil - Post-Doctoral
FAPESP's process: 19/04785-9 - Molecular dynamics study of the effect of flexibility over the melting point of ionic liquids
Grantee:Kalil Bernardino
Support Opportunities: Scholarships abroad - Research Internship - Post-doctor