Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters
The Basin Hopping search method is used to find the global minima (GM) and map the energy landscapes of thiocyanate-water clusters, (SCN−)(H2O)n with 3–50 water molecules, with empirical potentials describing the ion-water and water-water interactions. (It should be noted that beyond n = 23, the low...
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| Format: | Article |
| Language: | English |
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MDPI AG
2017-03-01
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| Series: | Inorganics |
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| Online Access: | http://www.mdpi.com/2304-6740/5/2/20 |
| _version_ | 1818018414889795584 |
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| author | Lewis C. Smeeton John C. Hey Roy L. Johnston |
| author_facet | Lewis C. Smeeton John C. Hey Roy L. Johnston |
| author_sort | Lewis C. Smeeton |
| collection | DOAJ |
| description | The Basin Hopping search method is used to find the global minima (GM) and map the energy landscapes of thiocyanate-water clusters, (SCN−)(H2O)n with 3–50 water molecules, with empirical potentials describing the ion-water and water-water interactions. (It should be noted that beyond n = 23, the lowest energy structures were only found in 1 out of 8 searches so they are unlikely to be the true GM but are indicative low energy structures.) As for pure water clusters, the low energy isomers of thiocyanate-water clusters show a preponderance of fused water cubes and pentagonal prisms, with the weakly solvated thiocyanate ion lying on the surface, replacing two water molecules along an edge of a water polyhedron and with the sulfur atom in lower coordinated sites than nitrogen. However, by comparison with Density Functional Theory (DFT) calculations, the empirical potential is found to overestimate the strength of the thiocyanate-water interaction, especially O–H⋯S, with low energy DFT structures having lower coordinate N and (especially) S atoms than for the empirical potential. In the case of these finite ion-water clusters, the chaotropic (“disorder-making”) thiocyanate ion weakens the water cluster structure but the water molecule arrangement is not significantly changed. |
| first_indexed | 2024-04-14T07:38:55Z |
| format | Article |
| id | doaj.art-dd10eb6cf1e940b5bd509dd47088c6a5 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-04-14T07:38:55Z |
| publishDate | 2017-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-dd10eb6cf1e940b5bd509dd47088c6a52022-12-22T02:05:35ZengMDPI AGInorganics2304-67402017-03-01522010.3390/inorganics5020020inorganics5020020Investigation of the Structures and Energy Landscapes of Thiocyanate-Water ClustersLewis C. Smeeton0John C. Hey1Roy L. Johnston2School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UKSchool of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UKSchool of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UKThe Basin Hopping search method is used to find the global minima (GM) and map the energy landscapes of thiocyanate-water clusters, (SCN−)(H2O)n with 3–50 water molecules, with empirical potentials describing the ion-water and water-water interactions. (It should be noted that beyond n = 23, the lowest energy structures were only found in 1 out of 8 searches so they are unlikely to be the true GM but are indicative low energy structures.) As for pure water clusters, the low energy isomers of thiocyanate-water clusters show a preponderance of fused water cubes and pentagonal prisms, with the weakly solvated thiocyanate ion lying on the surface, replacing two water molecules along an edge of a water polyhedron and with the sulfur atom in lower coordinated sites than nitrogen. However, by comparison with Density Functional Theory (DFT) calculations, the empirical potential is found to overestimate the strength of the thiocyanate-water interaction, especially O–H⋯S, with low energy DFT structures having lower coordinate N and (especially) S atoms than for the empirical potential. In the case of these finite ion-water clusters, the chaotropic (“disorder-making”) thiocyanate ion weakens the water cluster structure but the water molecule arrangement is not significantly changed.http://www.mdpi.com/2304-6740/5/2/20thiocyanatehydrated ionsmolecular clustersenergy landscapesglobal optimisation |
| spellingShingle | Lewis C. Smeeton John C. Hey Roy L. Johnston Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters Inorganics thiocyanate hydrated ions molecular clusters energy landscapes global optimisation |
| title | Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters |
| title_full | Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters |
| title_fullStr | Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters |
| title_full_unstemmed | Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters |
| title_short | Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters |
| title_sort | investigation of the structures and energy landscapes of thiocyanate water clusters |
| topic | thiocyanate hydrated ions molecular clusters energy landscapes global optimisation |
| url | http://www.mdpi.com/2304-6740/5/2/20 |
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