Premium
Ab Initio calculation of 19 F NMR chemical shielding for alkaline‐earth‐metal fluorides
Author(s) -
Cai ShuHui,
Chen Ztang,
Lu Xin,
Chen ZwWei,
Wan HuiLin
Publication year - 2001
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20010191204
Subject(s) - chemistry , chemical shift , alkaline earth metal , wave function , ab initio , core electron , metal , valence (chemistry) , basis set , electromagnetic shielding , computational chemistry , density functional theory , valence electron , electron , atomic physics , quantum mechanics , physics , organic chemistry
Gauge‐independent atomic orbital (GIAO) method at Hartree‐Fock (HF) and density functional theory (DFT) levels, respectively, was employed to calculate 19 F NMR chemical shieldings of solid state alkaline‐earth‐metal fluorides MF 2 (M = Mg, Ca, Sr, Ba). The results show that, although the calculated 19 F chemical shieldings tend to be larger than the experimental values, they have a fairly good linear relationship with the observed ones. The calculated results based on different combinations of basis sets show that the B3LYP (a hybrid of DFT with HF) predictions are greatly superior to the HF predictions. When a basis set of metal atom with effective core potential (ECP) has well representation of valence wavefunction, especially wavefunction of d component, and proper definition of core electron number, it can be applied to obtain 19 F chemical shielding which is close to that of all‐electron calculation. The variation of 19 F chemical shielding of alkaline‐earth‐metal fluorides correlates well with the lattice factor A/R 2 .