Investigating solvent effects on the magnetic properties of molybdate ions () with relativistic embedding
| Autor: | Valérie Vallet, André Severo Pereira Gomes, Małgorzata Olejniczak, Loïc Halbert |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
Aqueous solution
Materials science 010304 chemical physics Scalar (physics) Solvation 010402 general chemistry Condensed Matter Physics 01 natural sciences Molecular physics Atomic and Molecular Physics and Optics 0104 chemical sciences Ion 0103 physical sciences Electromagnetic shielding Physical and Theoretical Chemistry Solvent effects Relativistic quantum chemistry Electronic density |
| Zdroj: | International Journal of Quantum Chemistry. 120 |
| ISSN: | 1097-461X 0020-7608 |
| Popis: | We investigate the ability of mechanical and electronic density functional theory‐based embedding approaches to describe the solvent effects on nuclear magnetic resonance (NMR) shielding constants of the 95Mo 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 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. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Plný text