{"title":"磷酸三正丁酯与磷酸三异戊酯与 Th(IV)、U(VI) 和 Nd(III) 的络合:从理论到实验。","authors":"Aditya Ramesh Sachin, Balija Sreenivasulu, Cherukuri Venkata Siva Brahmananda Rao, Suresh Ammath, Gopinadhanpillai Gopakumar","doi":"10.1021/acs.jpca.4c02523","DOIUrl":null,"url":null,"abstract":"<p><p>The complexation behavior of tri-<i>iso</i>-amyl phosphate (TiAP) and tri-<i>n</i>-butyl phosphate (TBP) ligands with U(VI), Th(IV), and Nd(III) was investigated using density functional theory (DFT). Quantum chemical calculations yielded identical coordination geometries for TBP and TiAP complexes. Calculated complexation energies indicated a preferential extraction of U(VI) followed by Th(IV) over Nd(III), aligning with solvent extraction experiments conducted in the cross-current mode. Notably, during the separation of Th(IV) from RE(III), an increase in Th(IV) loading in the organic phase suppressed RE(III) extraction. Further analysis highlighted the crucial role of structural features (symmetry and dipole moment) in the extraction behavior of complexes. Energy decomposition analysis underscored the essential role of geometric strain and dispersion interaction energies in deciding the stability of the complexes.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Tri-<i>n</i>-butyl Phosphate vs Tri-<i>iso</i>-amyl Phosphate Complexation with Th(IV), U(VI), and Nd(III): From Theory to Experiment.\",\"authors\":\"Aditya Ramesh Sachin, Balija Sreenivasulu, Cherukuri Venkata Siva Brahmananda Rao, Suresh Ammath, Gopinadhanpillai Gopakumar\",\"doi\":\"10.1021/acs.jpca.4c02523\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The complexation behavior of tri-<i>iso</i>-amyl phosphate (TiAP) and tri-<i>n</i>-butyl phosphate (TBP) ligands with U(VI), Th(IV), and Nd(III) was investigated using density functional theory (DFT). Quantum chemical calculations yielded identical coordination geometries for TBP and TiAP complexes. Calculated complexation energies indicated a preferential extraction of U(VI) followed by Th(IV) over Nd(III), aligning with solvent extraction experiments conducted in the cross-current mode. Notably, during the separation of Th(IV) from RE(III), an increase in Th(IV) loading in the organic phase suppressed RE(III) extraction. Further analysis highlighted the crucial role of structural features (symmetry and dipole moment) in the extraction behavior of complexes. Energy decomposition analysis underscored the essential role of geometric strain and dispersion interaction energies in deciding the stability of the complexes.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpca.4c02523\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/9/6 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.4c02523","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/9/6 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Tri-n-butyl Phosphate vs Tri-iso-amyl Phosphate Complexation with Th(IV), U(VI), and Nd(III): From Theory to Experiment.
The complexation behavior of tri-iso-amyl phosphate (TiAP) and tri-n-butyl phosphate (TBP) ligands with U(VI), Th(IV), and Nd(III) was investigated using density functional theory (DFT). Quantum chemical calculations yielded identical coordination geometries for TBP and TiAP complexes. Calculated complexation energies indicated a preferential extraction of U(VI) followed by Th(IV) over Nd(III), aligning with solvent extraction experiments conducted in the cross-current mode. Notably, during the separation of Th(IV) from RE(III), an increase in Th(IV) loading in the organic phase suppressed RE(III) extraction. Further analysis highlighted the crucial role of structural features (symmetry and dipole moment) in the extraction behavior of complexes. Energy decomposition analysis underscored the essential role of geometric strain and dispersion interaction energies in deciding the stability of the complexes.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.