Original scientific paper

Computational Studies of Chemical Shifts Using Density Functional Optimized Geometries. II. Isotropic 1H and 13C Chemical Shifts and Substitutent Effects on 13C Shieldings in 2-Adamantanone

Dražen Vikić-Topić ; Rugjer Bošković Institute, NMR Center, R O. Box 180, HR-10002 Zagreb, Croatia
Ljupčo Pejov ; Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Cyril and Methodius University, P. O. Box 162, 91001 Skopje, Macedonia

Abstract

The 1H and 13C isotropic Chemical shifts and the substituent effects thereof (with respect to adamantane), computed at the HF, BLYP, B3LYP/6-3llG(d,p) as well as at MPW1PW91/6-3ll+G(2d,p) levels of theory with CSGT, GIAO and IGAIM algorithms, for the BLYP/6-31G(d,p) and B3LYP/6-31G(d,p) optimized geometries of 2-adamantanone are reported and compared with the experimental data. When absolute values of isotropic Chemical shifts (with respect to TMS) are in question, the MPW1PW91/6-3ll+G(2d,p) level leads to excellent agreement with the experiment, while the HF approach is superior to the BLYP and B3LYP ones. However, the substituent effects on 13C shieldings are better reproduced at the BLYP and B3LYP levels than at the HF level, while the MPW1PW91 approach is again significantly superior to ali the others, leading to excellent agreement with experimental data. The most probable reason for these findings may be the cancellation of errors arising from the inappropriate description of the paramagnetic contributions to the overall shielding tensor within the Kohn-Sham approach, and the more systematic nature of errors in DFT approaches. The isotropic Chemical shift values at all levels of theory, however, correlate excellently with the experimental data, the correlation being superior for DFT to the HF level of theory.

Keywords

magnetic shielding; ¹H and ¹³C isotropic Chemical shifts; ab initio calculations; density functional theory; 2-adamantanone

Hrčak ID:

131817

URI

https://hrcak.srce.hr/131817

Publication date:

2.4.2001.

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