Influence of Density Functionals and Basis Sets on One-Bond Carbon-Carbon NMR Spin-Spin Coupling Constants

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• 作者：R. Suard&iacute ; az ; C. Pé ; rez ; R. Crespo-Otero ; José ; M. Garc&iacute ; a de la Vega ; Jesú ; s San Fabiá ; n
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2008
• 出版时间：March 2008
• 年：2008
• 卷：4
• 期：3
• 页码：448 - 456
• 全文大小：184K
• 年卷期：v.4,no.3(March 2008)
• ISSN：1549-9626

文摘

The basis set and the functional dependence of one-bond carbon-carbon NMR spin-spin coupling constants (SSCC) have been analyzed using density functional theory. Four basissets (6-311G**, TZVP, EPR-III, and aug-cc-pVTZ-J) and four functionals (PBE, PW91, B3LYP,and B3P86) are tested by comparison with 70 experimental values corresponding to 49 moleculesthat represent multiple types of hybridization of the carbon atoms. The two hybrid functionalsB3P86 and B3LYP combined either EPR-III or aug-cc-pVTZ-J basis sets lead to the bestaccuracy of calculated SSCC. However, a simple linear regression allows for the obtaining ofscaled coupling constants that fit much better with the experimental data and where thedifferences between the different basis sets and/or functional results are significantly reduced.For large molecules the TZVP basis set can be an appropriate election presenting a goodcompromise between quality of results and computational cost.