title: Improvements in DFT Calculations of Spin-Spin Coupling Constants.
abstract: Different types of spin-spin coupling constants (SSCCs) for several representative small molecules are evaluated and analyzed using a combination of 10 exchange functionals with 12 correlation functionals. For comparison, calculations performed using MCSCF, SOPPA, other common DFT methods, and also experimental data are considered. A detailed study of the percentage of Hartree-Fock exchange energy in SSCCs and in its four contributions is carried out. From the above analysis, a combined functional formed with local Slater (34%), Hartree-Fock exchange (66%), and P86 correlation functional (S66P86) is proposed in this paper. The accuracy of the values obtained with this hybrid functional (mean absolute deviation of 4.5 Hz) is similar to that of the SOPPA method (mean absolute deviation of 4.6 Hz).
authors.affiliation: Departamento de Química Física Aplicada, Facultad de Ciencias, Universidad Autónoma de Madrid , 28049 Madrid, Spain.
authors.forename: J San
authors.initials: JS
authors.lastname: Fabián
authors.affiliation: Departamento de Química Física Aplicada, Facultad de Ciencias, Universidad Autónoma de Madrid , 28049 Madrid, Spain.
authors.forename: J M
authors.initials: JM
authors.lastname: García de la Vega
authors.affiliation: Departamento de Química Física, Unidad Asociada del CSIC and Instituto Universitario de Materiales, Universidad de Alicante , San Vicente del Raspeig, 03690 Alicante, Spain.
authors.forename: E
authors.initials: E
authors.lastname: San Fabián