Title :

Investigating solvent effects on the magnetic properties of molybdate ions (MoO₄^2-) with relativistic embedding

Author(s) :

Halbert, Loïc [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Olejniczak, Małgorzata [Auteur]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Severo Pereira Gomes, Andre [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]

Journal title :

International Journal of Quantum Chemistry

Pages :

e26207

Publisher :

Wiley

Publication date :

2020-11-01

ISSN :

0020-7608

English keyword(s) :

molybdate
shielding density
relativistic effects
solvation
NMR shielding
quantum embedding

HAL domain(s) :

Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

English abstract : [en]

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 ...
Show more >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.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

ANR Project :

Physiques et Chimie de l'Environnement Atmosphérique
ULNE

Comment :

16 pages, 6 figures

Collections :

• Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL