Publication
Title
Löwdin correlation energy density of the inhomogeneous electron liquid in some closed-shell molecules at equilibrium geometry
Author
Abstract
Using existing theoretical studies, we point out that the dominant variable in determining Lwdin correlation energies per electron Ec/N of isoelectronic series of molecules at equilibrium is the total number of electrons. This turns out to be Ec/N = -0.033 ± 0.003 a.u. for CH4, NH3, H2O and HF (N = 10), and Ec/N = -0.039 ± 0.007 for some 20 Si-containing molecules in the series SiXnYm. Following earlier work of March and Wind on atoms, some proposals are then made as to a possible explanation of such behaviour. A test is proposed, via low-order Mller-Plesset perturbation theory, as to whether the Lwdin correlation energy density åc(r) is, albeit approximately, a local functional åc(ñ) of the ground-state density for molecules at equilibrium. Such an LDA assumption would imply that åc(ñ) is quantitatively linear in ñ(r), for closed-shell molecules at equilibrium, at least for the light atomic components treated here. This, in turn implies that the dominant effect of the Lwdin correlation energy for closed-shell molecules at equilibrium is merely to shift the chemical potential.
Language
English
Source (journal)
Physics and chemistry of liquids. - London
Publication
London : 2008
ISSN
0031-9104
Volume/pages
46:5(2008), p. 484-490
ISI
000260382800003
Full text (Publisher's DOI)
UAntwerpen
Faculty/Department
Research group
Publication type
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Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
Identification
Creation 19.01.2009
Last edited 22.07.2017
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