Modelling the adiabatic connection in H2
Michael J. G. Peach, Andrew M. Teale, David J. Tozer, J. Chem. Phys., 126, 244104, 2007.
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The adiabatic connection formalism is an approach to developing exchange–correlation functionals via an integral over an interaction-strength coupling parameter that connects the non-interacting DFT system with the physical interacting system. The origins of this paper lay with the Mori-Sanchez, Cohen and Yang (MCY1 and 2) functionals, which gave us the impetus to investigate the limits of the accuracy achievable from a functional based on a Padé-approximation. To achieve this, we developed a procedure involving essentially exact full configuration-interaction calculations, to derive inputs for the Padé-approximation for H2 for a series of bond lengths. The conclusion is that the Padé-approximation is insufficiently flexible to allow an accurate description of the full potential energy curve. The procedure has subsequently been expanded by Teale and Helgaker, who were able to calculate accurate adiabatic connection data for all values of the coupling strength parameter.
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.
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