Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene Carbonate
Using ethylene carbonate as a sample solvent, we investigated two molecular parameters used to estimate the reduction potential of the solvent: electron affinity, and the energy of the lowest unoccupied molecular orbital (LUMO). The results showed that the values of these parameters are inconsistent...
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| Language: | English |
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MDPI AG
2022-12-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/23/24/15590 |
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| author | Andrzej Eilmes Piotr Kubisiak Piotr Wróbel |
| author_facet | Andrzej Eilmes Piotr Kubisiak Piotr Wróbel |
| author_sort | Andrzej Eilmes |
| collection | DOAJ |
| description | Using ethylene carbonate as a sample solvent, we investigated two molecular parameters used to estimate the reduction potential of the solvent: electron affinity, and the energy of the lowest unoccupied molecular orbital (LUMO). The results showed that the values of these parameters are inconsistent for a single ethylene carbonate molecule in vacuum calculations and in the continuous effective solvent. We performed a series of calculations employing explicit or hybrid (explicit/continuous) solvent models for aggregates of solvent molecules or solvated salt ions. In the hybrid solvent model, values of the two estimates extrapolated to an infinite system size converged to one common value, whereas the difference of 1 eV was calculated in the purely explicit solvent. The values of the gap between the highest occupied molecular orbital (HOMO) and the LUMO obtained in the hybrid model were significantly larger than those resulting from the explicit solvent calculations. We related these differences to the differences in frontier orbitals and changes of electron density obtained in the two solvent models. In the hybrid solvent model, the location of the additional electron in the reduced system usually corresponds to the LUMO orbital of the oxidized system. The presence of salt ions in the solvent affects the extrapolated values of the electron affinity and LUMO energy. |
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| id | doaj.art-6c3da7d1cf5d40cda95fa361bee55cef |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-09T16:19:42Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
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| series | International Journal of Molecular Sciences |
| spelling | doaj.art-6c3da7d1cf5d40cda95fa361bee55cef2023-11-24T15:24:10ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672022-12-0123241559010.3390/ijms232415590Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene CarbonateAndrzej Eilmes0Piotr Kubisiak1Piotr Wróbel2Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, PolandFaculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, PolandFaculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, PolandUsing ethylene carbonate as a sample solvent, we investigated two molecular parameters used to estimate the reduction potential of the solvent: electron affinity, and the energy of the lowest unoccupied molecular orbital (LUMO). The results showed that the values of these parameters are inconsistent for a single ethylene carbonate molecule in vacuum calculations and in the continuous effective solvent. We performed a series of calculations employing explicit or hybrid (explicit/continuous) solvent models for aggregates of solvent molecules or solvated salt ions. In the hybrid solvent model, values of the two estimates extrapolated to an infinite system size converged to one common value, whereas the difference of 1 eV was calculated in the purely explicit solvent. The values of the gap between the highest occupied molecular orbital (HOMO) and the LUMO obtained in the hybrid model were significantly larger than those resulting from the explicit solvent calculations. We related these differences to the differences in frontier orbitals and changes of electron density obtained in the two solvent models. In the hybrid solvent model, the location of the additional electron in the reduced system usually corresponds to the LUMO orbital of the oxidized system. The presence of salt ions in the solvent affects the extrapolated values of the electron affinity and LUMO energy.https://www.mdpi.com/1422-0067/23/24/15590ethylene carbonatereduction potentialsolvent modelquantum-chemical calculationsfrontier orbitals |
| spellingShingle | Andrzej Eilmes Piotr Kubisiak Piotr Wróbel Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene Carbonate International Journal of Molecular Sciences ethylene carbonate reduction potential solvent model quantum-chemical calculations frontier orbitals |
| title | Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene Carbonate |
| title_full | Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene Carbonate |
| title_fullStr | Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene Carbonate |
| title_full_unstemmed | Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene Carbonate |
| title_short | Explicit and Hybrid Solvent Models for Estimates of Parameters Relevant to the Reduction Potential of Ethylene Carbonate |
| title_sort | explicit and hybrid solvent models for estimates of parameters relevant to the reduction potential of ethylene carbonate |
| topic | ethylene carbonate reduction potential solvent model quantum-chemical calculations frontier orbitals |
| url | https://www.mdpi.com/1422-0067/23/24/15590 |
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