Investigating solvent effects on the magnetic properties of molybdate ions (MoO$_{4}^{2-}$) with relativistic embedding
Abstract
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.
- Publication:
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arXiv e-prints
- Pub Date:
- December 2019
- DOI:
- 10.48550/arXiv.1912.06192
- arXiv:
- arXiv:1912.06192
- Bibcode:
- 2019arXiv191206192H
- Keywords:
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- Physics - Chemical Physics
- E-Print:
- 14 pages, 6 figures