  Ab initio electronic structure methods give accurate results for small
systems, but do not scale well to large systems. Chemical insight tells us that
molecular functional groups will behave approximately the same way in all
molecules, large or small. This molecular similarity is exploited in
semiempirical methods, which couple simple electronic structure theories with
parameters for the transferable characteristics of functional groups. We propse
that high-level calculations on small molecules provide a rich source of
parametrization data. In principle, we can select a functional group, generate
a large amount of ab initio data on the group in various small-molecule
environments, and "mine" this data to build a sophisticated model for the
group's behavior in large molecules. This work details such a model for
electron correlation: a semiempirical, subsystem-based correlation functional
that predicts a subsystem's two-electron density as a functional of its
one-electron density. This model is demonstrated on two small systems: chains
of linear, minimal-basis (H-H)5, treated as a sum of four overlapping (H-H)2
subsystems; and the aldehyde group of a set of HOC-R molecules. The results
provide an initial demonstration of the feasibility of this approach.
