Investigating solvent effects on the magnetic properties of molybdate ions (MoO$_{4}^{2-}$) with relativistic embedding
| Autor: | Halbert, Loïc, Olejniczak, Małgorzata, Vallet, Valérie, Gomes, André Severo Pereira |
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| Rok vydání: | 2019 |
| Předmět: | |
| Zdroj: | International Journal of Quantum Chemistry, e26207 (2020) |
| Druh dokumentu: | Working Paper |
| DOI: | 10.1002/qua.26207 |
| Popis: | We investigate the ability of mechanical and electronic density functional theory (DFT)-based embedding approaches to describe the solvent effects on nuclear magnetic resonance (NMR) shielding constants of the $^{95}$Mo nucleus in the molybdate ion in aqueous solution. From the description obtained from calculations with two- and four-component relativistic Hamiltonians, we find that for such systems spin-orbit coupling effects are clearly important for absolute shielding values, but for relative quantities a scalar relativistic treatment provides a sufficient estimation of the solvent effects. We find that the electronic contributions to the solvent effects are relatively modest yet decisive to provide a more accurate magnetic response of the system, when compared to reference supermolecular calculations. We analyze the errors in the embedding calculations by statistical methods as well as through a real-space representation of NMR shielding densities, which are shown to provide a clear picture of the physical processes at play. Comment: 14 pages, 6 figures |
| Databáze: | arXiv |
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