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Non-empirical calculations of NMR indirect carbon-carbon coupling constants: 1. Three-membered rings
被引:74
作者:
Krivdin, LB
Sauer, SPA
Peralta, JE
Contreras, RH
机构:
[1] Tech Acad Angarsk, Dept Chem, Angarsk 665835, Russia
[2] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark
[3] Univ Buenos Aires, Dept Phys, RA-1428 Buenos Aires, DF, Argentina
关键词:
NMR;
C-13;
carbon-carbon spin-spin coupling constant;
three-membered rings;
RPA;
SOPPA;
DFT;
B3LYP;
basis set;
electronic correlation;
D O I:
10.1002/mrc.989
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
The carbon-carbon indirect nuclear spin-spin coupling constants in cyclopropane, aziridine and oxirane were investigated by means of ab initio calculations at the RPA, SOPPA and DFT/B3LYP levels. We found that the carbon-carbon couplings are by far dominated by the Fermi contact term. Our best SOPPA and DFT results are in a very good agreement with each other and with the experimental values, whereas calculations at the RPA level of theory strongly overestimate the carbon-carbon couplings. Significant differences in the basis set dependence of the calculated carbon-carbon coupling constants obtained with either wavefunction method, RPA or SOPPA, or the density functional method, DFT/B3LYP, are observed. The SOPPA results depend much more strongly on the quality of the basis set than the results of DFT/B3LYP calculations. The medium-sized core-valence basis sets cc-pCVTZ and even cc-pCVDZ were found to perform fairly well at the SOPPA level for the one-bond carbon-carbon couplings investigated here. Copyright (C) 2002 John Wiley Sons, Ltd.
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页码:187 / 194
页数:8
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