Relativistic Frozen Density Embedding calculations of solvent effects on the NMR shielding constants of transition metal nuclei

Abstract

Nuclear Magnetic Resonance (NMR) shielding constants of transition metals in solvated complexes are computed at the relativistic density functional theory (DFT) level. The solvent effects evaluated with subsystem-DFT approaches are compared with the reference solvent shifts predicted from supermolecular calculations. Two subsystem-DFT approaches are analyzed -- in the standard frozen density embedding (FDE) scheme the transition metal complexes are embedded in an environment of solvent molecules whose density is kept frozen, in the second approach the densities of the complex and of its environment are relaxed in the "freeze-and-thaw" procedure. The latter approach improves the description of the solvent effects in most cases, nevertheless the FDE deficiencies are rather large in some cases.

References in corpus (6)

• The DIRAC code for relativistic molecular calculations
• Quantum embedding theories
• Subsystem Density-Functional Theory as an Effective Tool for Modeling Ground and Excited States, their Dynamics, and Many-Body Interactions
• PCMSolver: an Open-Source Library for Solvation Modeling
• On the calculation of second-order magnetic properties using subsystem approaches in the relativistic framework
• Investigating solvent effects on the magnetic properties of molybdate ions (MoO${}_4^{2-}$) with relativistic embedding