Title
Löwdin correlation energy density of the inhomogeneous electron liquid in some closed-shell molecules at equilibrium geometry
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
London ,
Subject
Physics
Chemistry
Source (journal)
Physics and chemistry of liquids. - London
Volume/pages
46(2008) :5 , p. 484-490
ISSN
0031-9104
ISI
000260382800003
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
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.
E-info
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