Approximate Analytical Solutions of the Thomas–Fermi and

Thomas–Fermi–Dirac Equations and Calculation of Diamagnetic Susceptibilities

P. Csavinszky

Citation: The Journal of Chemical Physics 50, 3629 (1969); doi: 10.1063/1.1671596
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 50. NUMBER 8 15 APRIL 1969

Approximate Analytical Solutions of the Thomas-Fermi and Thomas-Fermi-Dirac

Equations and Calculation of Diamagnetic Susceptibilities
P. CSAVINSZKY
TRW Systems, Redondo Beach, Califo,nia 90278
(Received 30 December 1968)

Recently derived approximate analytical solutions of the Thomas-Fermi (TF) and Thomas-Fermi-Dirac
(TFD) equations, together with the latter's analytical extension involving the correlation effect, are used
for calculating the diamagnetic susceptibilities of Ar, Kr, and Xe. It is concluded that the agreement of
the calculated susceptibilities with experimental data, especially in the case of the TFD model, is com-
parable in accuracy with quantum-mechanical calculations.

I. INTRODUCTION analytical solution of the TF equation in connection

with the calculation of other atomic constants such as
In a recent paper Dehn and Mulayl have compared
the diamagnetic susceptibilities of atoms.
the experimental diamagnetic susceptibilities of atoms
with values calculated by using approximate atomic A. Thomas-Fermi Approximation
wavefunctions. They have concluded that wave-
functions composed of Slater-type functions with In terms of the dimensionless variable
optimized orbital exponents, such as given by Clementi x=r/p, = 4 (2Z/9"r) l/a,./as, (1)
et al. 2 •8 for most of the periodic table, seem to give the
best agreement over the entire range of atomic numbers where r is the distance from the nucleus, in units of the
considered (Z=2 to 86). Bohr radius as, and Z the atomic number, the TF
The purpose of the present paper is to show that a theory states5 •6 that the electron density of neutral
recently derived approximate analytical solution' of atoms is given by
the Thomas-Fermi equation/· 6 and especially its p= (Z/47rp,I) (rp/X)8/ 2. (2)
analytical extension7 involving the exchange and cor-
relation effects of the electrons, gives an agreement In Eq. (2) the quantity rp is the universal solution of
with experimental data which is comparable in accuracy the TF equation for neutral atoms. Using for rp the
with the quantum-mechanical calculations. approximate analytical solution, obtained from the
variational principle, we have
II. THEORY
rp= [a exp( -ax) +b exp( -,8x)], (3)
The approximate analytical solution' of the TF where
equation for atoms is based on a variational principle. a=O.7111, a=O.175,
It represents a significant improvement in the radial
b=O.2889, ,8=1.6625. (4)
electron density distribution since it leads to a radial
electron density which decreases exponentially with the According to theory9 the diamagnetic susceptibility
distance from the nucleus instead of the inverse fourth per gram-atom is calculated from
power decreases which is obtained from the numerical
solution of the TF equation. The improvement in the x.= -L(eN6moc2 ) (ro2), (5)
electron density is reflected in the calculated total where (ro2) is defined9 by
ionization energies of neutral atoms, which have been
found' in better agreement with the experimental
values than the values obtained from the numerical
(ro2)= f pr2dv=47r [0o pr4dr. (6)

solution of the TF equation. It is, therefore, of interest In Eqs. (5) and (6) L is the Loschmidt-Avogadro
to inquire about the reliability of the approximate number, eo is the electronic charge, mo is the electron
mass, c is the velocity of light, and ro denotes the radius
1 J. T. Dehn and L. N. Mulay, J. Chem. Phys. 48, 4910 (1968). of the atom considered. For a neutral atom in the TF
2 E. Clementi and D. L. Raymondi, J. Chem. Phys. 38, 2686 theory ro= 00, while in the TFD theory ro=constant.
(1963) .
• E. Clementi, D. L. Raymondi, and W. P. Reinhardt, J. Chem. Using Eqs. (1)-(3) one finds from Eq. (6) that
Phys. 47, 1300 (1967).
4 P. Csavinszky, Phys. Rev. 166, 53 (1968). (ro2) =zp,2r (i)
6 For a review of the subject see: P. Gombas. Encyclopedia of
Physics, S. Fliigge, Ed. (Springer-Verlag, Berlin, 1956), Vol. a8 3a2b 3ab2 b8 )
(7)
XXXVI, p. 1200.
6 For a review of the subject see: P. Gombas, Die statistische
X ( (3a)7/2 + (2a+,8)7/2 + (a+2,8)7/2 + (3,8)7/2 '
Theorie des Atoms und ih,e Anwendungen (Springer-Verlag,
Vienna, 1949), p. 300. where rei) =¥-rr.
7 P. Csavinszky, J. Chem. Phys. 50, 2476 (1969).
8 See Ref. 5, p. 132; or Ref. 6, p. 54. 9 See Ref. 5, p. 189ff; or Ref. 6, p. 299ff.
3629
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 3630 P. CSAVINSZKY

TABLE I. Diamagnetic susceptibilities In the TFD theory the electron density is given by
(in units of 1()8 cm3/g-atom).
p= (Z/47rp.8) (1/1" /x), (10)
Ar Kr Xe
where 1/1" denotes the second derivative of 1/1 with
XupU -19.6 -28.8 -43.9 respect to x.
xG(TF) -18.8 -23.6 -27.1 Using the technique developed in connection with an
approximate analytical solution of the TF equation for
I Xe.ptl-xG(TF) I 0.8 5.2 16.8
positive ions,12 the author has also obtained an ap-
xG(TFD) -22.8 -35.9 -44.8 proximate analytical solution of the TFD equation.7
I xUPu-xG(TFD) I 3.2 7.1 0.9 The latter is of the form
xG(TFDG) -21.0 -34.2 -43.2 I/I=q,+rt, (11)
I XuPtl-xG(TFDG) I 1.4 5.4 0.7 where q, is given in Eqs. (3) and (4), and
x(QM) -17.4 -26.8 -42.6
to to to rt = Kl[exp (mIx) -exp(1n2x) J
-18.3 -27.9 -38.9
+",[exp( -2ax) -exp(1n2x)J. (12)
I XuPtl-x(QM) I 2.2 2.0 1.3
to to to In Eq. (12) the quantities Kl, ml, 'In2, and", are
1.3 0.9 5.0
constants. Their numerical values for Ar, Kr, and Xe
are listed in Table II.
Considering Eq. (10) partial integration of Eq. (6)
Considering Eqs. (4) and (7) one finds that Eq. (S) leads tolS
leads to
x= -7.16X1O-&Zl/8. (8)
(ro2) =Zp.2 [[I/I'xB]O"'0-[31/1x2Jo"'0+6 [0 I/IxdX] , (13)
Values calculated from Eq. (8) for Ar, Kr, and Xe
are denoted by xa(TF) and listed in Table 1. Also where Xo is the dimensionless radius of the atom con-
listed are the experimental values,lo which are denoted sidered and the symbol [F(x) Jo"'o stands for F(Xo)-
by Xexptl, and the "best" quantum-mechanical values, F(o). The numerical values of Xo for Ar, Kr, and Xe
which are denoted by x(QM). A comparison of the are collected in Table II.
calculated and measured values shows that the mag- Considering that one of the boundary conditions in
nitude of the former is smaller than that of the latter. the TFD theory isll
The agreement is good for Ar and Kr but poor for Xe.
(14)
The magnitude of the discrepancy is clearly a function
of Z and increases with Z. This is in contrast to the where
.80=!(3/47r2Z2) 1/3 =0.2118/Z2/3, (1S)
quantum-mechanical values, whose magnitudes are
smaller than those of the experimental values but where and the subsidiary (normalization) condition for
the magnitude of the discrepancy is roughly constant. neutral atoms is'·l
It should be emphasized that Eq. (8), based on the
Xo!/I'(Xo) -1/I(Xo) =0, (16)
variational solution of the TF equation for neutral
atoms, is a significant improvement over the result one can bring Eq. (13) to the form
derived from the numerical solution of the TF equa-
tion. By making use of an analytical approximation
of the numerical solution of the TF equation, Sommer-
(r02)=Zp.2 (6 [0 I/Ixdx- i,802Xos). (17)
feld has found9 that
Using Eq. (11) the evaluation of the integral in Eq.
X = -31 X 1o-&Zl/3. (9) (17) is trivial and the end result is omitted here.
The numerical values of the diamagnetic suscepti-
A comparison of Eq. (9) with the experimental
bilities of Ar, Kr, and Xe are calculated from Eqs. (S)
values shows that Eq. (9) overestimates the mag-
and (17). They are listed with the symbol Xa(TFD)
nitude of the diamagnetic susceptibilities by about a
in Table 1. A comparison of the calculated values with
factor of 4 for Ar and Kr and by about a factor of 2.S
the experimental values shows that the magnitude of
for Xe.
the former is larger than that of the latter. While the
B. Thomas-Fermi-Dirac Approximation magnitude of the discrepancy between calculated and
measured values is slightly larger for Ar and Kr than
The exchange effect between electrons of parallel spin in the TF case, it is noteworthy that for Xe it is much
has been introduced into the TF model by Dirac. ll smaller. The above comparison shows that the overall

10 For references see Ref. 1. 12 P. Csavinszky, J. Chem. Phys. 50, 1176 (1969).
11 See Ref. 5, p. 139ff; or Ref. 6, p. 77ff. 18 See Ref. 6, p. 232ff.

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 SOLUTIONS OF THOMAS-FERMI-DIRAC EQUATIONS 3631
TABLE II. Quantities appearing in the approximate analytical solutions of the TFD and TFDG equations.

Ar Kr Xe
TFD TFDG TFD TFDG TFD TFDG

KI and KI 6. 82XI0-s 1. llXlO-1 1. 23XlQ-s 1.91XIQ-s 4.58XIQ-' 7. 16XIQ-8

mI.! and ml,! ±0.537 ±0.551 ±0.497 ±0.506 ±0.481 ±0.487
wandw -0.360 -0.384 -0.277 -0.298 -0.234 -0.253
Xo and Xo 16.45 15.48 19.75 18.92 21.52 20.73

agreement between theory and experiment for the
range of atomic nwnbers considered is, as expected,
better in the TFD approximation than in the TF
approximation.
C. Thomas-Fermi-Dirac-Gombas (TFDG)
Approximation
The correlation effect between electrons of anti-
parallel spin has been introduced into the TFD theory
by Gombas.14 He has shown that, to a very good ap-
proximation, all formal results of the TFD theory can
be retained by replacing the constant Po by Po, defined14
by
Po = 0.2394/Z2/8. (18)
The above also holds concerning the approximate
analytical solution7 of the TFD G equation. This is of
the form
(19)
with
7f=KI [exp(nitx) -exp(~x) J
+c;,[exp( -2ax) -exp(~x)].
The numerical values of the constants !iI, nit, ~
and c;, are shown in Table II. [In the previous work7
Eq. (20) has been determined only for XeJ.
14 See Ref. 5, p. 145ffj or Ref. 6, p. 96ff.
Using Eqs. ( 19), (20), and ( 17), the diamagnetic
susceptibilities for Ar, Kr, and Xe have been cal-
culated from Eq. (5). The nwnerical values, denoted
by Xa (TFD G), are collected in Table I. It is seen from
Table I that, relative to the TFD model, consideration
of the correlation effect leads to a reduction in the
magnitude of the diamagnetic susceptibilities. It is
also seen that this change in the magnitude of the
calculated values is in the desired direction, improving
the agreement of the theoretical values with the
experimental values. Furthermore, Table I also shows
that, with the exception of Kr, the agreement of the
TFD G diamagnetic susceptibilities with the experi-
mental ones is just as good, or even better, than the
agreement of the quantum-mechanical values with the
experimental values.
nI. CONCLUSIONS
The good agreement between theoretical and experi-
mental diamagnetic susceptibilities is in support of the
conclusion that the statistical theory, based on the ap-
(20) proximate analytical solutions of the various models,
is a useful tool for calculating atomic constants. Such
an approach is of importance either in obtaining
mathematically simpler formulas than the quantum-
mechanical ones or in dealing with problems where no
quantum-mechanical results are available.

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