Comparative assessment of a new nonempirical density functional:molecules and hydrogen-bonded complexes

摘要

A comprehensive study is undertaken to assess the nonempirical meta-generalized gredient approximation (MGGA)of Tao,Perdew,Staroverov,and Scuseria (TPSS)against 14 common exchange-correlation energy functionals.Principal results are presented in te form of statistical summaries fo deviations from experiment for the G3/99 test set (223 enthalpies of formation,86 ionization potentials,58 electron affinities,8 proton affinities)and three additional test sets ivolving 96 bond lengths,82 harmonic vibrational frequencies,and 10 hydrogen-bonded complexes,all computed usign the 6-311++G(3DF,3PD)basis.The tpss functional matches,or exceeds in accuracy all prior nanempirical constructions and,unlike esmiempirical functionals,consistently provides a high-qualitly description of diverse systems and properties.The computational cost of self-consistent MGGA is not required.A one-parameter global hybrid version of the TPSS functional is introduced and shown to give further improvement for most properties.