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Title
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Löwdin correlation energy density of the inhomogeneous electron liquid in some closed-shell molecules at equilibrium geometry
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Author
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Abstract
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| 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. |
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Language
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English
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Source (journal)
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Physics and chemistry of liquids. - London
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Publication
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London
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2008
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ISSN
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0031-9104
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DOI
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10.1080/00319100701790069
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Volume/pages
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46
:5
(2008)
, p. 484-490
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ISI
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000260382800003
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Full text (Publisher's DOI)
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