| Full text | |
| Author(s): |
Bernardino, Kalil
[1]
;
Goloviznina, Kateryna
[2]
;
Gomes, Margarida Costa
[2]
;
Padua, Agilio A. H.
[2]
;
Ribeiro, Mauro C. C.
[1]
Total Authors: 5
|
| Affiliation: | [1] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Lab Espectroscopia Mol, Av Prof Lineu Prestes 748, BR-05508000 Sao Paulo, SP - Brazil
[2] Univ Lyon, CNRS, ENS Lyon, Lab Chim, F-69364 Lyon - France
Total Affiliations: 2
|
| Document type: | Journal article |
| Source: | Journal of Chemical Physics; v. 152, n. 1 JAN 7 2020. |
| Web of Science Citations: | 0 |
| Abstract | |
Numerous combinations of cations and anions are possible for the production of ionic liquids with fine-tuned properties once the correlation with the molecular structure is known. In this sense, computer simulations are useful tools to explain and even predict the properties of ionic liquids. However, quantum mechanical methods are usually restricted to either small clusters or short time scales so that parameterized force fields are required to study the bulk liquids. In this work, a method is proposed to enable a comparison between the quantum mechanical system and both polarizable and nonpolarizable force fields by means of the calculation of free energy surfaces for the translational motion of the anion around the cation in gas phase. This method was tested for imidazolium-based cations with 3 different anions, {[}BF4](-), {[}N(CN)(2)](-), and {[}NTf2](-). Better agreement was found with the density functional theory calculations when polarizability is introduced in the force field. In addition, the ion pair free energy surfaces reproduced the main structural patterns observed in the first coordination shell in molecular dynamics simulations of the bulk liquid, proving to be useful probes for the liquid phase structure that can be computed with higher level methods and the comparison with forcefields can indicate further improvements in their parameterization. (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 |