Title




Exchange energy density and some approximate exchange potentials obtained from HartreeFock theory of the ground state of the Be atom


Author






Abstract




HartreeFock (HF) theory of the ground state of the Be atom is used to calculate first the exchange energy density e(x)(r) from the Dirac density matrix. Beyond r = 2a(0), with a(0) = h(2)/me(2), epsilon (x)(r) rapidly approaches the general asymptotic form 1/2e(2)rho (r)/r, with p(r) the HF electronic density. The nuclear cusp condition 1/epsilon (x)(r) partial derivative epsilon (x)/partial derivativer /(r >0) = 2Z/a(0) with atomic number Z = 4, is also accurately satisfied by the present numerical data. Since a quantum Monte Carlo (QMC) exchangecorrelation potential exists for the Be atom, we have compared this with (a) the Slater potential VSL(r) = 2 epsilon (x)(r)/rho (r) and (b) the HarbolaSahni form. Both have the main features of the QMC exchangecorrelation potential, though the magnitude of VSL(r) at r = 0 is too large by some 16%. We have also studied how well these two approximate HF exchange potentials fare when inserted into the LevyPerdew relation between the total exchange energy and the 'viriallike' form involving the gradient of the exchange potential. (C) 2001 Elsevier Science B.V. All rights reserved. 


Language




English


Source (journal)




Chemical physics letters.  Amsterdam, 1967, currens


Publication




Amsterdam
:
2001


ISSN




00092614
[print]
18734448
[online]


DOI




10.1016/S00092614(01)005619


Volume/pages




343
:12
(2001)
, p. 166170


ISI




000170144200025


Full text (Publisher's DOI)






Full text (publisher's version  intranet only)





