Date of Award
Doctor of Philosophy (PhD)
Chemistry and Chemical Biology
Paul W. Ayers
Approximating the exchange-correlation energy in density functional theory (DFT) is a crucial task. As the only missing element in the Kohn-Sham DFT, the search for better exchange-correlation functionals has been an active field of research for fifty years. Many models and approximations are known and they can be summarized in what is known as the Jacob’s ladder. All the functionals in that ladder are local in the sense that they rely on the information of only one electronic coordinate. That is, even though the exchange-correlation hole, the cornerstone in density functional theory, is a two-electron coordinate quantity, one of the coordinates is averaged over in “Jacob’s ladder functionals.” This makes the calculations considerably more efficient. On the other hand, some of the important constraints on the form of the exchange-correlation functional become inaccessible in the one-point forms. The violation of these constraints leads to functionals plagued by systematic errors, leading to qualitatively incorrect descriptions of some chemical and physical processes.
In this thesis the idea of a weighted density approximation (WDA) is explored. More specifically, a symmetric and normalized two-point functional is proposed for the exchange-correlation energy functional. The functional is based entirely on the hole for the uniform electron gas. By construction, these functionals fulfill two of the most important constraints: the normalization of the exchange-correlation hole and the uniform electron gas limit. The findings suggest that we should pursue a whole new generation of “new Jacob’s ladder” functionals.
A further step was considered. Given the relevance of the long-range behavior of the exchange-correlation hole, a study of the electronic direct correlation function was performed. The idea was to build up the long-range character of the hole as convoluted pieces of the simple and short-ranged direct correlation function. This direct correlation function provides better results, at least for the correlation energy in the spin-polarized uniform electron gas.
The advantage of one-point functionals is their computational efficiency. We therefore attempted to develop new methods that mitigate the relative computational inefficiency of two-point functionals. This led to new methods for evaluating the six-dimensional integrals that are inherent to the exchange-correlation energy.
Cuevas-Saavedra, Rogelio, "Weighted Density Approximations for Kohn-Sham Density Functional Theory" (2012). Open Access Dissertations and Theses. Paper 6998.
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