Basis set dependence of 1H–X spin–spin coupling constants in non-empirical pure DFT framework, X = 1H, 13C, 19F, 35Cl: Case of CHCl=CH–CF3 stereoisomers

Abstract

A collection of indirect spin–spin coupling constants (SSCCs) including 3J(H,H), nJ(C,H) (n = 1–3), nJ(H,F) (n = 3, 4), and nJ(H,Cl) (n = 2, 3) were assessed in the non-empirical density functional theory (DFT) framework for the stereoisomers of CHCl=CH–CF3. The present paper puts on view the DFT method, the basis set, and the stereoisomer dependences of the SSCCs. The basis sets cc-pVXZ and aug-cc-pVXZ (X = D, T, Q, and 5) were used to handle these nuclear parameters. The DFT scheme through the non-empirical exchange–correlation functionals Perdew–Burke–Ernzerhof, Perdew–Kurth–Zupan–Blaha exchange–correlation functional, Tao, Perdew, Staroverov, and Scuseria (PBEPBE, PKZBPKZB, and TPSSTPSS) was benchmarked by the computationally expensive second-order polarization propagator approximation method to provide a very good correlation of the nuclear SSCC parameters. This method was corrected by the relativistic, vibrational, and solvent effects. The findings show that the SSCCs are highly sensitive to the basis set. The convergence of SSCCs to the basis set limit is achieved for some coupling constants and tends to achieve for the others, except for 2J(H,Cl) and 3J(H,Cl). The functionals PBEPBE and PKZBPKZB appear as the excellent deal to assess all the coupling constants of this study. nJ(H,F) (n = 3, 4) and nJ(H,Cl) (n = 2, 3) are very well described by all the three competitive functionals and the different quality X of the basis set in regard to the experimental results and the reference values.