INVESTIGADORES
AUCAR Ignacio Agustin
artículos
Título:
Relativistic and quantum electrodynamics effects on NMR shielding tensors of Tl X ( X = H, F, Cl, Br, I, At) molecules
Autor/es:
KOZIOL, KAROL; AUCAR, I. AGUSTÍN; GAUL, KONSTANTIN; BERGER, ROBERT; AUCAR, GUSTAVO A.
Revista:
JOURNAL OF CHEMICAL PHYSICS
Editorial:
AMER INST PHYSICS
Referencias:
Lugar: New York; Año: 2024 vol. 161
ISSN:
0021-9606
Resumen:
The results of relativistic calculations of nuclear magnetic resonance shielding tensors (σ) for the thallium monocation (Tl+), thallium hydride (TlH), and thallium halides (TlF, TlCl, TlBr, TlI, and TlAt) are presented as obtained within a four-component polarization propagator formalism and a two-component linear response approach within the zeroth-order regular approximation. In addition to a detailed analysis of relativistic effects performed in this work, some quantum electrodynamical (QED) effects on those nuclear magnetic resonance shieldings and other small contributions are estimated. A strong dependence of σ(Tl) on the bonding partner is found, together with a very weak dependence of QED effects with them. In order to explain the trends observed, the excitation patterns associated with relativistic ee (or paramagnetic-like) and pp (or diamagnetic-like) contributions to σ are analyzed. For this purpose, the electronic spin-free and spin-dependent contributions are separated within the two-component zeroth-order regular approximation, and the influence of spin–orbit coupling on involved molecular orbitals is studied, which allows for a thorough understanding of the underlying mechanisms.