A new all-round density functional based on spin states and S(N)2 barriers.
We report here a new empirical density functional that is constructed based on the performance of OPBE and PBE for spin states and S(N)2 reaction barriers and how these are affected by different regions of the reduced gradient expansion. In a previous study [Swart, Sola, and Bickelhaupt, J. Comput. Methods Sci. Eng. 9, 69 (2009)] we already reported how, by switching between OPBE and PBE, one could obtain both the good performance of OPBE for spin states and reaction barriers and that of PBE for weak interactions within one and the same (SSB-sw) functional. Here we fine tuned this functional and include a portion of the KT functional and Grimme's dispersion correction to account for pi-pi stacking. Our new SSB-D functional is found to be a clear improvement and functions very well for biological applications (hydrogen bonding, pi-pi stacking, spin-state splittings, accuracy of geometries, reaction barriers).
Swart
Marcel
M
Departament de Química and Institut de Química Computacional, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalunya, Spain. marcel.swart@icrea.es
Solà
Miquel
M
Bickelhaupt
F Matthias
FM
D003198:Computer Simulation; D006801:Humans; D006860:Hydrogen Bonding; D011789:Quantum Theory; D013816:Thermodynamics