On the accuracy of the GIAO-DFT calculation of 15N NMR chemical shifts of the nitrogen-containing heterocycles--a gateway to better agreement with experiment at lower computational cost

On the accuracy of the GIAO-DFT calculation of 15N NMR chemical shifts of the nitrogen-containing heterocycles--a gateway to better agreement with experiment at lower computational cost

Copyright © 2014 John Wiley & Sons, Ltd.

Bibliographische Detailangaben
Veröffentlicht in:Magnetic resonance in chemistry : MRC. - 1985. - 52(2014), 5 vom: 26. Mai, Seite 222-30
1. Verfasser: Samultsev, Dmitry O (VerfasserIn)
Weitere Verfasser: Semenov, Valentin A, Krivdin, Leonid B
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2014
Zugriff auf das übergeordnete Werk:Magnetic resonance in chemistry : MRC
Schlagworte:Journal Article Research Support, Non-U.S. Gov't 15N NMR GIAO-DFT azines azoles chemical shift locally dense basis set magnetic shielding constant Azoles mehr... Hydrazines Nitrogen Isotopes Pyridazines
Beschreibung
Zusammenfassung:Copyright © 2014 John Wiley & Sons, Ltd.
The main factors affecting the accuracy and computational cost of the gauge-independent atomic orbital density functional theory (GIAO-DFT) calculation of (15)N NMR chemical shifts in the representative series of key nitrogen-containing heterocycles--azoles and azines--have been systematically analyzed. In the calculation of (15)N NMR chemical shifts, the best result has been achieved with the KT3 functional used in combination with Jensen's pcS-3 basis set (GIAO-DFT-KT3/pcS-3) resulting in the value of mean absolute error as small as 5 ppm for a range exceeding 270 ppm in a benchmark series of 23 compounds with an overall number of 41 different (15)N NMR chemical shifts. Another essential finding is that basically, the application of the locally dense basis set approach is justified in the calculation of (15)N NMR chemical shifts within the 3-4 ppm error that results in a dramatic decrease in computational cost. Based on the present data, we recommend GIAO-DFT-KT3/pcS-3//pc-2 as one of the most effective locally dense basis set schemes for the calculation of (15)N NMR chemical shifts
Beschreibung:Date Completed 24.11.2014
Date Revised 07.04.2014
published: Print-Electronic
Citation Status MEDLINE
ISSN:1097-458X
DOI:10.1002/mrc.4055