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PHYSICS LETTERS

2 July 1984

ENERGY RELATIONS IN THE DENSITY FUNCTIONAL THEORY OF d-DIMENSIONAL HEAVY POSITIVE IONS N.H. MARCH Theoretical Chemistry Department, University of Oxford, 1 South Parks Road, Oxford OX1 3TG, UK Received 15 May 1984

By means of the virial theorem, the total energy E, eigenvalue sum E s and chemical potential ta are related in a heavy positive ion in d dimensions. The scaling properties of these quantities in two dimensions are thereby established.

In recent work [1], the eigenvalue sum E s and the chemical potential # have been studied for N electrons moving independently in bare point charge potentials, as a function of dimensionality d. In particular, for the ratio Es/N# in the asymptotic limit of large N, the following result was established [ 1] :

Es/NP = d(4 - d)/(4 + 2d - d 2 ) .

(1)

The purpose of the present letter is to include the selfconsistent field, which screens the outermost electrons from the full attraction of the bare point charge of magnitude Ze say. Below, use will be made of the density functional theory at the level in which exchange and correlation effects are neglected. This is known to be an adequate approximation for dimensionality d = 3 in the limit of sufficiently heavy positive ions [2] The Euler equation expressing the constancy of the chemical potential ta in space may be written [3]

p = 5T/So(r) + Vn(r) + Ve(r ) .

where Uen is the electron-nuclear potential energy f p Vndr while the electron-electron potential energy 1 1 Uee Is ~fPVedr, the factor ~ as usual preventing double counting of electron-electron interactions. Earlier, the writer [4] studied the kinetic term in eq. (3), and demonstrated by means of some specific examples that for large N the local density, T h o m a s Fermi, contribution gave the dominant term, the nonlocal corrections affecting only lower order terms in N. Thus, denoting the total kinetic energy in the local density limit by T, eq. (3) for Np simplifies in d dimensions to N p = ( 1 + 2/cOT+ Uen + 2Uee. (4)

It is obvious that the eigenvalue sum E s is simply T + Uen + 2Uee and using this result in eq. (4) yields

Nla = (2/d)T + E s .

(5)

(2)

At this stage, we invoke the virial theorem, which for the present problem reads [5] 2T + (d - 2) (Uen + Uee) = 0 , while the total energy E is evidently E = T + Uen + Uee. (7) (6)

Here TIp] is the kinetic energy as a functional of the electron density o(r), V e is the screening contribution of the electron cloud to the total Hartree potential energy, while Vn represents the bare nucleus. We now multiply eq. (2) by p and integrate over all space. Using the normalization condition that there are N electrons in the charge cloud, plus the constancy of/a in space, we find immediately 5T Np = , J/ ' p ~--~) d,r + Ven + 2Uee , 186 (3)

Eliminating the potential energy terms between eqs. (6) and (7) yields then T = [(2 - d)/(4 - d)] E , which includes the familiar result T = - E for three dimensions. By substituting for T from eq. (8) into 0.3750601/84/$ 03.00 Elsevier Science Publishers B.V. (North-Holland Physics Publishing Division) (8)

E = ( E s - N O ) a ( 4 - d ) / 2 ( a - 2)

PHYSICS LETTERS

O = (aE/aN)z,

(9)

follows, which reduces to the result E = a (E s _ NO) given previously by the writer for d = 3 [6]. As well as being correct asymptotically for large N in the familiar three-dimensional case, the result (9) can be applied for d/> 5. For d = 4, the numerator evidently vanishes; an immediate consequence of the virial theorem in the form (7) leading to E --- 0. For d = 2, considered in more detail below, both the numerator and denominator in eq. (9) become zero. It is worth adding here relations for the potential energy contributions: Uee - NO = [(d 2 _ 2d - 4)/d(4 - d)] E , Uen + N o = [(4 + 4 d - d 2 ) / d ( 4

o(Z, N) = Z f ~(N/Z ) .

(14)

Returning to the virial theorem (6) we note that when d = 2 this implies T = 0 which is to be interpreted to mean that, to leading order in N for large N, the potential energy U = Uen + Uee dominates T i n the two-dimensional case; i.e. E = U in the asymptotic limit. From eq. (5) it then follows that, for d = 2,

E s = NO = ZNf'2(N/Z) = Z 2 [(N/Z)f'2(N/Z)] ,

(15)

-d)]E.

(10)

Of course, the explicit solution of the case d = 3 has already been obtained by numerical integration of the appropriate non-linear Thomas-Fermi equation and the total energy is known to take the form [3]

with the same type o f scaling therefore as in eq. (I 2) for the total energy E 2. For the neutral atom case N = Z and d = 2, Kventsel and Katriel [10] argue that the chemical potential O is zero, which would then yield

E = U = - U e e = ~Uen. 1

(16)

13 = Z7 /3 f 3 ( N / Z ) ,

(11)

The potential energy relations exhibited in eq. (16) are, for d = 2, the results o f putting O = 0 in eqs. (10) for general dimensionality. Part o f this work was carried out during a visit to UCSB, California. The writer wishes to thank Professor J.R. Schrieffer for his very kind hospitality.

where/'3 is a numerically known function, with analytic representations near N / Z = 0 and also around the neutral atom limit where N / Z tends to unity [7]. For this three-dimensional case, March and Pucci [8] have fully described how one can characterize the total ground state energy by means o f the chemical potential. We shall conclude by discuksing the two-dimensional case in a little more detail. As seems to have been noted first by Lennard-Jones and Woods [9], and exploited by subsequent workers [10], the differential equation for the self-consistent potential is then linear. Kventsel and Katriel [ 10] have solved this equation in terms of modified Bessel functions and using their results we have established that, corresponding to eq. (11), the two-dimensional scaling property of the total energy of heavy positive ions is

References

[1] N.H. March (1984), to be published. [2] J.M.CI Scott, Philos. Mag. 43 (1952) 859. [3] S. Lundqvist and N.H. March, eds., Theory of the inhomogeneous electron gas (Plenum, New York, 1983). [4] N.H. March, J. Chem. Phys. 74 (1981) 2376. [5] M. Parrinello and N.H. March, J. Phys. C9 (1976) L147. [6] N.H. March, J. Chem. Phys. 72 (1980) 1994. [7] Y. Tal and M. Levy, Phys. Rev. A23 (1981) 408; N.H. March, J. Chem. Phys. 76 (1982) 1430; J.P. Grout, N.M. March and Y. Tal. J. Chem. Phys. 79 (1983) 331. [8] N.H. March and R. Pucei, J. Chem. Phys. 78 (1983) 2480. [9] J.E. Lennard-Jones and H.J. Woods, Proc. R. Soc. 120 (1928) 727. [10] G.F. Kventsel and J. Katriel, Phys. Rev. A24 (1981) 2299.

E 2 (Z, N ) = Z 2 f 2 ( N / Z ) .

Using the "thermodynamic relation" [3]

(I 2)

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