A comparison of density functional methods for the calculation of phosphorus-31 NMR chemical shifts
A comparison of density functional methods for the calculation of phosphorus-31 NMR chemical shifts
复制标题
计算磷 31 NMR 化学位移的密度泛函方法的比较
DOI：
10.1039/b000461h
复制
发表时间：
2000
影响因子：
3.3
通讯作者：
C. Wüllen
中科院分区：
文献类型：
--
作者：
C. Wüllen
31
P
磷化合物PX 3（X=H、F、Cl、CH 3、iC 3 H 7和OCH 3）、OPX 3的NMR化学位移
（X= CH 3
和OCH 3），Si（PH 2）4，Cr（CO 5）（PH 3），PX 4+（X=H，CH 3），PF 6 −，P4和PN已经用各种方法计算过。
密度泛函方法以及在Hartree-Fock和MP2水平上，使用IGLO和GIAO
除了MP2（只有GIAO可用）和Wilson，Amos和Handy最近提出的新方法（WAH，GIAO不可用）之外，引入分布式规范源的变体。除了PCl 3
和PN，所有密度
函数方法实现了相当的准确性，优于Hartree-Fock，与MP2相似。对于PCl 3和PN，WAH方法导致实质性的改进。GIAO和IGLO的结果如下：
可比的准确性。PN在其实验条件下的绝对磁屏蔽的数值基准值
平衡值，并与文献数据进行了比较。了理论
分析表明，使用的近似
使他们的方法失去了规范不变性。
31
P
NMR chemical shifts for the phosphorus compounds PX3 (X=H, F, Cl, CH3, iC3H7 and OCH3), OPX3
(X=CH3
and OCH3), Si(PH2)4, Cr(CO5)(PH3), PX4+ (X=H, CH3), PF6−, P4 and PN have been calculated with various
density functional methods as well as at the Hartree–Fock and MP2 level, using both the IGLO and GIAO
variants of introducing distributed gauge origins except for MP2 (only GIAO available) and the new method proposed recently by Wilson, Amos and Handy (WAH, GIAO not available). Except for PCl3
and PN, all density
functional approaches achieve comparable accuracy, better than Hartree–Fock and similar to MP2. For PCl3 and PN, the WAH method leads to a substantial improvement. The GIAO and IGLO results are of
comparable accuracy. Numerical benchmark values for the absolute magnetic shielding of PN at its experimental
equilibrium value are presented and compared with literature data. A theoretical
analysis reveals that the approximation used
by WAH makes their method lose gauge invariance.