Assessing a new nonempirical density functional: difficulties in treating pi-conjugation effects.
The reliability of the Tao-Perdew-Staroverov-Scuseria (TPSS) exchange-correlation functional for the description of conjugation effects in model pi-conjugated systems has been thoroughly assessed through the calculation of torsion energy profiles. The functional reproduces qualitatively the shape of torsional potentials but, interestingly, the mixing of TPSS and exact exchange governs the quantitative results: thus, well-defined hybrid extensions of the functional are consistently employed to improve the results. The hybrid approaches led to more accurate descriptions of conjugation effects but, however, the finest performance along the whole range of dihedral angles was obtained by a customized mixing of pure or hybrid TPSS functionals and wave function methods in a multicoefficient fashion. Despite the successful construction of this nonempirical functional, higher rungs of the ladder of methods in which TPSS is based are hoped to reduce the errors with respect to reference data for pi-conjugated systems.
Sancho-García
J C
JC
Departamento de Química Física, Universidad de Alicante, E-03080 Alicante, Spain. jc.sancho@ua.es