全氟化合物的¹⁹F核磁共振化学位移的密度泛函理论-广义膺势法计算

DFT-GIAO calculations of 19F NMR chemical shifts for perfluoro compounds.

作者信息

Fukaya Haruhiko, Ono Taizo

机构信息

Institute for Structural and Engineering Materials, National Institute of Advanced Industrial Science and Technology (AIST), Shimoshidami, Moriyama-ku, Nagoya 463-8560, Japan.

出版信息

J Comput Chem. 2004 Jan 15;25(1):51-60. doi: 10.1002/jcc.10339.

DOI:10.1002/jcc.10339

PMID:14634993

Abstract

The (19)F NMR shieldings for 53 kinds of perfluoro compounds were calculated by the B3LYP-GIAO method using the 6-31G(d), 6-31+G(d), 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p), 6-311++G(d,p), 6-311G(2d,2p), 6-311++G(2d,2p), 6-311++G(2df,2p), 6-311++G(3d,2p), and 6-311++G(3df,2p) basis sets. The diffuse functions markedly reduce the difference between the calculated and experimental chemical shifts. The calculations using the 6-31++G(d,p) basis set give the chemical shifts within 10 ppm deviations from experimental values except for the fluorine nuclei attached to an oxygen atom, a four- and a six-coordinated sulfur atom, and FC(CF(3))(2) attached to a sulfur atom.

摘要

采用B3LYP-GIAO方法，使用6-31G(d)、6-31+G(d)、6-31G(d,p)、6-31++G(d,p)、6-311G(d,p)、6-311++G(d,p)、6-311G(2d,2p)、6-311++G(2d,2p)、6-311++G(2df,2p)、6-311++G(3d,2p)和6-311++G(3df,2p)基组，计算了53种全氟化合物的(19)F NMR屏蔽常数。漫射函数显著降低了计算化学位移与实验化学位移之间的差异。除了与氧原子、四配位和六配位硫原子相连的氟核以及与硫原子相连的FC(CF(3))(2)外，使用6-31++G(d,p)基组进行的计算得到的化学位移与实验值的偏差在10 ppm以内。