Core-electron contributions to the molecular magnetic response
No hay miniatura disponible
Archivos
Fecha
2022-04-19
Autores
Orozco-Ic, Mesías
Charistos, Nickolas D.
Muñoz-Castro, Alvaro
Islas, Rafael
Sundholm, Dage
Merino, Gabriel
Profesor/a Guía
Facultad/escuela
Idioma
en
Título de la revista
ISSN de la revista
Título del volumen
Editor
Royal Society of Chemistry
Nombre de Curso
Licencia CC
ATTRIBUTION-NONCOMMERCIAL 3.0 UNPORTED
CC BY-NC 3.0
Deed
Licencia CC
https://creativecommons.org/licenses/by-nc/3.0/
Resumen
Orbital contributions to the magnetic response depend on the method used to compute them. Here, we show that dissecting nuclear magnetic shielding tensors using natural localized molecular orbitals (NLMOs) leads to anomalous core contributions. The arbitrariness of the assignment might significantly affect the interpretation of the magnetic response of nonplanar molecules such as C60 or [14]helicene and the assessment of their aromatic character. We solve this problem by computing the core- and σ-components of the induced magnetic field (and NICS) and the magnetically induced current density by removing the valence electrons (RVE). We estimate the core contributions to the magnetic response by performing calculations on the corresponding highly charged molecules, such as C6H630+ for benzene, using gauge-including atomic orbitals and canonical molecular orbitals (CMOs). The orbital contributions to nuclear magnetic shielding tensors are usually estimated by employing a natural chemical shielding (NCS) analysis in NLMO or CMO bases. The RVE approach shows that the core contribution to the magnetic response is small and localized at the nuclei, contrary to what NCS calculations suggest. This may lead to a completely incorrect interpretation of the magnetic σ-orbital response of nonplanar structures, which may play a major role in the overall magnetic shielding of the system. The RVE approach is thus a simple and inexpensive way to determine the magnetic response of the core- and σ-electrons. © 2022 The Royal Society of Chemistry.
Notas
Indexación: Scopus.
Palabras clave
Chemical analysis, Magnetic shielding, Magnetism, Molecules, Tensors
Citación
Physical Chemistry Chemical Physics, Volume 24, Issue 20, Pages 12158 - 12166, 19 April 2022
DOI
10.1039/d1cp05713h