Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field
This work aims at unravelling the interactions in magnetic ionic liquids (MILs) by applying Symmetry-Adapted Perturbation Theory (SAPT) calculations, as well as based on those to set-up a polarisable force field model for these liquids. The targeted MILs comprise two different cations, namely: 1-but...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-09-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/18/5526 |
| _version_ | 1797517990329057280 |
|---|---|
| author | Iván González-Veloso Nádia M. Figueiredo M. Natália D. S. Cordeiro |
| author_facet | Iván González-Veloso Nádia M. Figueiredo M. Natália D. S. Cordeiro |
| author_sort | Iván González-Veloso |
| collection | DOAJ |
| description | This work aims at unravelling the interactions in magnetic ionic liquids (MILs) by applying Symmetry-Adapted Perturbation Theory (SAPT) calculations, as well as based on those to set-up a polarisable force field model for these liquids. The targeted MILs comprise two different cations, namely: 1-butyl-3-methylimidazolium ([Bmim]<sup>+</sup>) and 1-ethyl-3-methylimidazolium ([Emim]<sup>+</sup>), along with several metal halides anions such as [FeCl<sub>4</sub>]<sup>−</sup>, [FeBr<sub>4</sub>]<sup>−</sup>, [ZnCl<sub>3</sub>]<sup>−</sup> and [SnCl<sub>4</sub>]<sup>2−</sup> To begin with, DFT geometry optimisations of such MILs were performed, which in turn revealed that the metallic anions prefer to stay close to the region of the carbon atom between the nitrogen atoms in the imidazolium fragment. Then, a SAPT study was carried out to find the optimal separation of the monomers and the different contributions for their interaction energy. It was found that the main contribution to the interaction energy is the electrostatic interaction component, followed by the dispersion one in most of the cases. The SAPT results were compared with those obtained by employing the local energy decomposition scheme based on the DLPNO-CCSD(T) method, the latter showing slightly lower values for the interaction energy as well as an increase of the distance between the minima centres of mass. Finally, the calculated SAPT interaction energies were found to correlate well with the melting points experimentally measured for these MILs. |
| first_indexed | 2024-03-10T07:23:54Z |
| format | Article |
| id | doaj.art-2326e151ad8943ec9dda75c875cdc96a |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T07:23:54Z |
| publishDate | 2021-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-2326e151ad8943ec9dda75c875cdc96a2023-11-22T14:24:27ZengMDPI AGMolecules1420-30492021-09-012618552610.3390/molecules26185526Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force FieldIván González-Veloso0Nádia M. Figueiredo1M. Natália D. S. Cordeiro2LAQV@REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169-007 Porto, PortugalLAQV@REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169-007 Porto, PortugalLAQV@REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169-007 Porto, PortugalThis work aims at unravelling the interactions in magnetic ionic liquids (MILs) by applying Symmetry-Adapted Perturbation Theory (SAPT) calculations, as well as based on those to set-up a polarisable force field model for these liquids. The targeted MILs comprise two different cations, namely: 1-butyl-3-methylimidazolium ([Bmim]<sup>+</sup>) and 1-ethyl-3-methylimidazolium ([Emim]<sup>+</sup>), along with several metal halides anions such as [FeCl<sub>4</sub>]<sup>−</sup>, [FeBr<sub>4</sub>]<sup>−</sup>, [ZnCl<sub>3</sub>]<sup>−</sup> and [SnCl<sub>4</sub>]<sup>2−</sup> To begin with, DFT geometry optimisations of such MILs were performed, which in turn revealed that the metallic anions prefer to stay close to the region of the carbon atom between the nitrogen atoms in the imidazolium fragment. Then, a SAPT study was carried out to find the optimal separation of the monomers and the different contributions for their interaction energy. It was found that the main contribution to the interaction energy is the electrostatic interaction component, followed by the dispersion one in most of the cases. The SAPT results were compared with those obtained by employing the local energy decomposition scheme based on the DLPNO-CCSD(T) method, the latter showing slightly lower values for the interaction energy as well as an increase of the distance between the minima centres of mass. Finally, the calculated SAPT interaction energies were found to correlate well with the melting points experimentally measured for these MILs.https://www.mdpi.com/1420-3049/26/18/5526magnetic ionic liquidsSAPTenergy decompositionpolarisable force field |
| spellingShingle | Iván González-Veloso Nádia M. Figueiredo M. Natália D. S. Cordeiro Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field Molecules magnetic ionic liquids SAPT energy decomposition polarisable force field |
| title | Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field |
| title_full | Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field |
| title_fullStr | Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field |
| title_full_unstemmed | Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field |
| title_short | Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field |
| title_sort | unravelling the interactions of magnetic ionic liquids by energy decomposition schemes towards a transferable polarizable force field |
| topic | magnetic ionic liquids SAPT energy decomposition polarisable force field |
| url | https://www.mdpi.com/1420-3049/26/18/5526 |
| work_keys_str_mv | AT ivangonzalezveloso unravellingtheinteractionsofmagneticionicliquidsbyenergydecompositionschemestowardsatransferablepolarizableforcefield AT nadiamfigueiredo unravellingtheinteractionsofmagneticionicliquidsbyenergydecompositionschemestowardsatransferablepolarizableforcefield AT mnataliadscordeiro unravellingtheinteractionsofmagneticionicliquidsbyenergydecompositionschemestowardsatransferablepolarizableforcefield |