Scaling dynamical correlation energy from density functional theory correlation functionals.
The scaling of dynamical correlation energy in molecules obtained by the correlation functionals of density functional theory (DFT) is examined. The approach taken is very similar to the scaled external correlation method of Brown and Truhlar but is based on the observation that DFT correlation functionals, especially the LYP, appear to represent the dynamical portion of the correlation energy in molecules. We examine whether higher accuracy in atomization energies can be gained by scaling without significant deterioration of the structural and spectroscopic properties of the molecules using four DFT functionals (BLYP, OLYP, B3LYP, and O3LYP) on 19 molecules including the six molecule AE6 database, the latter being representative of a much larger, 109 molecule training set. We show that, with molecule specific scale factors, nearly perfect agreement with experiment can be achieved in atomization energies without increasing the average errors in other molecular properties relative to the DFT calculation. We further show that it is possible to find optimal scale factors which reduce the mean unsigned error per bond to levels comparable to those of some multilevel multicoefficient methods.
Ramachandran
B
B
Chemistry, College of Engineering and Science, Louisiana Tech University, Ruston, Louisiana 71272, USA. ramu@latech.edu