Localized Orbital Corrections: A new approach to obtaining quantitative accuracy in DFT thermochemistry calculations

Richard Freisner, Columbia University

We have developed a new approach to density functional theory which involves the use of localized orbital corrections (LOC). The B3LYP-LOC methodology achieves an average error of 0.8 kca/mole for the G3 set of atomization energy test cases developed by Pople and coworkers, in comparison to the 4.8 kca/mole average error of B3LYP and the 1.0 kcal/molle average error of G3 theory. Similar improvements have been made in electron affinities and ionization potentials. The correction scheme costs essentially no computational effort and has been implemented in an automated fashion for second and third row atoms. Work is currently ongoing to extend the method to transition states and transition metal containing systems. We will discuss the underlying ideas of the methodology, which provide insight into the dominant errors in current density functional approaches, as well as presenting a range of numerical results.

The P/T Colloquium is
typically held each
Thursday, 3:45–5:00 PM.

Collaborations 3:15 PM.