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.

arXiv comment14 pages, 6 figures

References in corpus (4)

• Mayavi: a package for 3D visualization of scientific data
• Quantum embedding theories
• Spin in Density-Functional Theory
• On the calculation of second-order magnetic properties using subsystem approaches in the relativistic framework

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