Differential correlation energy

Koopmans theorem also implies that the eigenvalue associated with the HF LUMO may be equated with the EA. However, in the case of EAs errors associated with basis set incompleteness and differential correlation energies do not cancel, but instead they reinforce one another, and as a result EAs computed by this approach are usually entirely untrustworthy. 

The MP2 calculations were intended to provide an estimate of the differential correlation energy associated with various valence-state configurations. Accordingly, the ls-2p(Co) and ls(N) cores were not active in the MP2 calculations. Extension of the Co core to include the 3s/3p shell was found to yield results similar to those based on the ls-2p core, and some of the results reported below were obtained at this level. 

The accuracy of the MP2 results rests on the fact that the differential correlation energy associated with the unpaired electron is reasonably small in the case that the unpaired electron is loosely-bound. Let us denote this differential correlation energy for M as... 

When is an eigenvalue of r(.B),. E is a pole. The corresponding operator, r(JS), is nonlocal and energy-dependent. In its exact limit, it incorporates all relaxation and differential correlation corrections to canonical orbital energies. A normalized DO is determined by an eigenvector of T Epou) according to... 

The zero differential overlap approximation can be applied in the localized representation. This was demonstrated by calculating for C H, CioTfio and C14//14, respectively the total energy corrections and the pair correlation energies through second and third order in different approximations. When the strongly local contributions were only... 

The answer is yes, in a very general way, as has been discussed before [62,63]. Consider any parameter in the external potential, called y. For definiteness, we choose the internuclear separation in a diatomic molecule. Then the exchange-correlation energy depends parametrically on this quantity. Now imagine making an infinitesimal change in y. The differential change in is... 

The local ground-state correlation potential is defined in RDFT as the functional derivative of Eq.(7) with respect to p. When infinitesimal variation of occupation numbers is allowed, a more practical definition follows from the fact that the unsymmetrical energy formuala used to construct Eq.(7) is itself a Landau functional of the occupation numbers [19]. Correlation energies of Landau quasiparticles, expressed as diagonal elements of a one-electron Hamiltonian matrix, are defined by differentiating with respect to occupation numbers to give... 

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