Repositorio Institucional
Repositorio Institucional
CONICET Digital
  • Inicio
  • EXPLORAR
    • AUTORES
    • DISCIPLINAS
    • COMUNIDADES
  • Estadísticas
  • Novedades
    • Noticias
    • Boletines
  • Ayuda
    • General
    • Datos de investigación
  • Acerca de
    • CONICET Digital
    • Equipo
    • Red Federal
  • Contacto
JavaScript is disabled for your browser. Some features of this site may not work without it.
  • INFORMACIÓN GENERAL
  • RESUMEN
  • ESTADISTICAS
 
Artículo

Large long-range F-F indirect spin-spin coupling constants. Prediction of measurable F-F couplings over a few nanometers

Provasi, Patricio FedericoIcon ; Aucar, Gustavo AdolfoIcon ; Sauer, Stephan P. A.
Fecha de publicación: 05/2004
Editorial: American Chemical Society
Revista: Journal of Physical Chemistry A
ISSN: 1089-5639
e-ISSN: 1520-5215
Idioma: Inglés
Tipo de recurso: Artículo publicado
Clasificación temática:
Otras Ciencias Físicas

Resumen

Large long-range indirect nuclear spin coupling constants are of great interest for quantum computers. But they are rarely observed and are usually considered very small, unless the coupled nuclear spins are proximate in space. Looking for counterexamples, we have calculated F−F couplings in four different series of acyclic hydrocarbons (alkanes, conjugated polyenes, conjugated polyynes, and cumulenes) where the coupled fluorine nuclei are separated by up to 11 bonds or 1.4 nm. The calculations were carried out at the level of the second-order polarization propagator approximation using locally dense basis sets. This approach has, in recent years, been shown to be particularly successful in reproducing indirect nuclear spin−spin couplings in organic molecules. We find that the F−F couplings in saturated alkanes diminish very quickly with the number of bonds between the coupled fluorine atoms, whereas in the conjugated polyenes and in particular polyynes the F−F couplings can be transmitted over much longer distances. We predict that the F−F coupling over 9 bonds or 1.1 nm is 12 Hz in (1E,3E,5E,7E)-1,8-difluoroocta-1,3,5,7-tetraene and the coupling over 11 bonds or 1.4 nm is 7 Hz in difluorodecapentayne. Analyzing the four Ramsey contributions, we find that the F−F couplings in the polyenes are dominated by the spin−dipolar term, which is known to be favored by π-electronic systems, whereas in the case of the polyynes the orbital paramagnetic terms make the largest contributions, although the spin−dipolar and the Fermi contact contributions are also significant.
Palabras clave: Nmr , Spin-Spin Coupling Constant , Long Range Coupling Constant , Fluorine-Fluorine
Ver el registro completo
 
Archivos asociados
Thumbnail
 
Tamaño: 107.3Kb
Formato: PDF
.
Descargar
Licencia
info:eu-repo/semantics/openAccess Excepto donde se diga explícitamente, este item se publica bajo la siguiente descripción: Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Unported (CC BY-NC-SA 2.5)
Identificadores
URI: http://hdl.handle.net/11336/22290
URL: http://pubs.acs.org/doi/abs/10.1021%2Fjp048686v
DOI: http://dx.doi.org/10.1021/jp048686v
Colecciones
Articulos(IMIT)
Articulos de INST.DE MODELADO E INNOVACION TECNOLOGICA
Citación
Provasi, Patricio Federico; Aucar, Gustavo Adolfo; Sauer, Stephan P. A.; Large long-range F-F indirect spin-spin coupling constants. Prediction of measurable F-F couplings over a few nanometers; American Chemical Society; Journal of Physical Chemistry A; 108; 25; 5-2004; 5393-5398
Compartir
Altmétricas
 

Enviar por e-mail
Separar cada destinatario (hasta 5) con punto y coma.
  • Facebook
  • X Conicet Digital
  • Instagram
  • YouTube
  • Sound Cloud
  • LinkedIn

Los contenidos del CONICET están licenciados bajo Creative Commons Reconocimiento 2.5 Argentina License

https://www.conicet.gov.ar/ - CONICET

Inicio

Explorar

  • Autores
  • Disciplinas
  • Comunidades

Estadísticas

Novedades

  • Noticias
  • Boletines

Ayuda

Acerca de

  • CONICET Digital
  • Equipo
  • Red Federal

Contacto

Godoy Cruz 2290 (C1425FQB) CABA – República Argentina – Tel: +5411 4899-5400 repositorio@conicet.gov.ar
TÉRMINOS Y CONDICIONES