Zero-point vibrational effects on proton shieldings:: Functional-group contributions from ab initio calculations

被引:123
作者
Ruud, K
Åstrand, PO
Taylor, PR
机构
[1] Univ Calif San Diego, San Diego Supercomp Ctr, La Jolla, CA 92093 USA
[2] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA
[3] Riso Natl Lab, Dept Mat Res, DK-4000 Roskilde, Denmark
关键词
D O I
10.1021/ja004160m
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We investigate the effects of zero-point vibrational motion on the nuclear magnetic shielding constants of a large number of organic molecules. The vibrational corrections include anharmonic contributions from the potential energy surface and harmonic contributions from the curvature of the property surface. Particular attention is paid to vibrational corrections to hydrogen shielding constants where we show that vibrational corrections may be substantial, ranging from about +0.50 to -0.70 ppm, and thus demonstrating that ignoring these effects may give errors in the chemical shifts by more than 1 ppm in certain extreme cases. These effects can therefore not be neglected when comparing calculated results with experiment, not even for the chemical shifts. However, we also demonstrate that the vibrational corrections to the hydrogen shieldings are to a large extent transferable from one molecule to another. We have tabulated functional vibrational corrections to the hydrogen shieldings, based on results for more than 35 molecules. Unfortunately, no similar transferability has been observed for the vibrational corrections to shielding constants of other nuclei such as carbon, nitrogen, or oxygen.
引用
收藏
页码:4826 / 4833
页数:8
相关论文
共 51 条