TY - JOUR
T1 - Influence of density functionals and basis sets on one-bond carbon-carbon NMR spin-spin coupling constants
AU - Suardíaz, R.
AU - Pérez, C.
AU - Crespo-Otero, R.
AU - De La Vega, José M. García
AU - Fabián, Jesús San
PY - 2008/2/21
Y1 - 2008/2/21
N2 - 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 basis sets (6-311G**, TZVP, EPR-III, and aug-cc-pVTZ-J) and four functional (PBE, PW91, B3LYP, and B3P86) are tested by comparison with 70 experimental values corresponding to 49 molecules that represent multiple types of hybridization of the carbon atoms. The two hybrid functionals B3P86 and B3LYP combined either EPR-III or aug-cc-pVTZ-J basis sets lead to the best accuracy of calculated SSCC. However, a simple linear regression allows for the obtaining of scaled coupling constants that fit much better with the experimental data and where the differences 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 good compromise between quality of results and computational cost.
AB - 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 basis sets (6-311G**, TZVP, EPR-III, and aug-cc-pVTZ-J) and four functional (PBE, PW91, B3LYP, and B3P86) are tested by comparison with 70 experimental values corresponding to 49 molecules that represent multiple types of hybridization of the carbon atoms. The two hybrid functionals B3P86 and B3LYP combined either EPR-III or aug-cc-pVTZ-J basis sets lead to the best accuracy of calculated SSCC. However, a simple linear regression allows for the obtaining of scaled coupling constants that fit much better with the experimental data and where the differences 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 good compromise between quality of results and computational cost.
UR - http://www.scopus.com/inward/record.url?scp=58149152660&partnerID=8YFLogxK
U2 - 10.1021/ct7003287
DO - 10.1021/ct7003287
M3 - Article
AN - SCOPUS:58149152660
SN - 1549-9618
VL - 4
SP - 448
EP - 456
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 3
ER -