We have calculated the (13) C NMR chemical shifts of a large ensemble of halogenated organic molecules (81 molecules for a total of 250 experimental (13) C NMR data at four different levels of theory), ranging from small rigid organic compounds, used to benchmark the performance of various levels of theory, to natural substances of marine origin with conformational degrees of freedom. Carbon atoms bonded to heavy halogen atoms, particularly bromine and iodine, are known to be rather challenging when it comes to the prediction of their chemical shifts by quantum methods, due to relativistic effects. In this paper, we have applied the state-of-the-art four-component relativistic density functional theory for the prediction of such NMR properties and compared the performance with two-component and nonrelativistic methods. Our results highlight the necessity to include relativistic corrections within a four-component description for the most accurate prediction of the NMR properties of halogenated organic substances.

Casella, G., Bagno, A., Komorovsky, S., Repisky, M., Saielli, G. (2015). Four-Component Relativistic DFT Calculations of (13) C Chemical Shifts of Halogenated Natural Substances. CHEMISTRY, 21, 18834-18840 [10.1002/chem.201502252].

Four-Component Relativistic DFT Calculations of (13) C Chemical Shifts of Halogenated Natural Substances

CASELLA, Girolamo;
2015-01-01

Abstract

We have calculated the (13) C NMR chemical shifts of a large ensemble of halogenated organic molecules (81 molecules for a total of 250 experimental (13) C NMR data at four different levels of theory), ranging from small rigid organic compounds, used to benchmark the performance of various levels of theory, to natural substances of marine origin with conformational degrees of freedom. Carbon atoms bonded to heavy halogen atoms, particularly bromine and iodine, are known to be rather challenging when it comes to the prediction of their chemical shifts by quantum methods, due to relativistic effects. In this paper, we have applied the state-of-the-art four-component relativistic density functional theory for the prediction of such NMR properties and compared the performance with two-component and nonrelativistic methods. Our results highlight the necessity to include relativistic corrections within a four-component description for the most accurate prediction of the NMR properties of halogenated organic substances.
2015
Settore CHIM/02 - Chimica Fisica
Casella, G., Bagno, A., Komorovsky, S., Repisky, M., Saielli, G. (2015). Four-Component Relativistic DFT Calculations of (13) C Chemical Shifts of Halogenated Natural Substances. CHEMISTRY, 21, 18834-18840 [10.1002/chem.201502252].
File in questo prodotto:
File Dimensione Formato  
CHEMISTRY_FOUR_COMPONENT_2015.pdf

Solo gestori archvio

Descrizione: Articolo principale
Dimensione 507.22 kB
Formato Adobe PDF
507.22 kB Adobe PDF   Visualizza/Apri   Richiedi una copia
chem_201502252_sm_miscellaneous_information.pdf

Solo gestori archvio

Descrizione: Materiale supplementare
Dimensione 508.74 kB
Formato Adobe PDF
508.74 kB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/152127
Citazioni
  • ???jsp.display-item.citation.pmc??? 2
  • Scopus 27
  • ???jsp.display-item.citation.isi??? 26
social impact