Adiabatic connection forms in density functional theory: H2 and the He isoelectronic series

Michael J. G. Peach, Adam M. Miller, Andrew M. Teale, David J. Tozer, J. Chem. Phys., 129, 064105, 2008.


In a follow-up to our earlier work on the adiabatic connection, we consider a wide selection of two-electron systems, in an investigation of the accuracy achievable from a series of simple approximate forms. In particular, we were able to improve on the results of our earlier study, by using a simple exponential form.

Further information, including details of subsequent work in this area, can be found on the adiabatic connection research page. For the abstract, and access to the full text, see below.


Full configuration interaction (FCI) data are used to quantify the accuracy of approximate adiabatic connection (AC) forms in describing two challenging problems in density functional theory—the singlet ground state potential energy curve of H2 in a restricted formalism and the energies of the helium isoelectronic series, H to Ne8+. For H2, an exponential-based form yields a potential energy curve that is virtually indistinguishable from the FCI curve, eliminating the unphysical barrier to dissociation observed previously with a [1,1]-Padé-based form and with the random phase approximation. For the helium isoelectronic series, the Padé-based form gives the best overall description, followed by the exponential form, with errors that are orders of magnitude smaller than those from a standard hybrid functional. Particular attention is paid to the limiting behavior of the AC forms with increasing bond distance in H2 and increasing atomic number in the isoelectronic series; several forms describe both limits correctly. The study illustrates the very high quality results that can be obtained using exchange-correlation functionals based on simple AC forms, when near-exact data are used to determine the parameters in the forms.

Leave a Comment

Your email address will not be published. Required fields are marked *