Book alonso & finn volume 3.

capitulate 4

section 4.1 Introduction

All atoms – except hydrogen and certain ions of the light elements – contain several electrons.
Therefore it may seen that the one-electron problem studied in the previous chapter is of little
practical value. However, an understanding of the properties of one-electron atoms is very helpful
in analyzing many-electron atoms.

The first difficulty with the many-electron atom is the impossibility of describing the motion of
each individual electron because, in addition to considering the electron interaction of each electron
with the nucleus, we must consider the mutual interactions among the electrons. Thus the potential
energy of the whole atom is:
equation 4.1

The last summation provides a coupling int the motion of the electrons, and hence we cannot
consider each electron as moving independently of the others. Any modification in the motion of
one electron must, of necessity, affect the motion of all the other electrons. Therefore we cannot
speak of the individual energy of each electron but only of the energy of the whole atom (or ion).
For the same reason, we do not speak of a wave function for each electron, but only a wave function
for the complete atom.

The problem of many electron cannot be solved exactly; therefore certain approximations are
required. We shall illustrate these approximations by discussing the helium atom.

See picture 4.1

4.2 The Helium Atom

Of all the many-electrons atoms, the simplest are those with tow electrons, such as the negative
hydrogen ion H- (Z = 1), the helium atom He (Z = 2), the singly ionized lithium atom Li+ (Z = 3),
and so on. The potential energy of the electron in this case is:
Picture 4-1 and equation 4-2

The first two terms correspond to the attraction between the nucleus and each of the electron and the
last term to the repulsion between the two electrons. Even for this relatively simple problem of only
two electrons, it is impossible to solve Schrodinger's equation exactly; it is necessary to make
several approximations. Since the mathematical discussion of heliumlike atoms is beyond the scope
of this book, we shall limit ourselves to a physical description, followed, in example 4.2, by a brief
explanation of how the energy is a calculated.

As a first approximation, we may ignore the last term (or the electron-electron interaction term) in
eq.(4.2). This is equivalent to assuming that each electron moves independently of the other. Thus
we may call this approximation the independent-particle model. Therefore the motion of each
electron can be described by hydrogenlike wave functions of the type (x), specified by the orbital
quantum numbers n, l, ml. The energy of the electronic motion in the ground state, n=1 (if we set
z=2 in eq. 3.5) would be Ehe= 2 x (-54,4eV) = -108,8eV. The experimental value, however, is Ehe=
-78,98eV. The reason for this is that we neglected the repulsion of the two electrons, which tends to
raise the energy of the atom.
We can improve our approximation by considering the perturbation of the electronic motion caused
by the mutual interaction of the two electrons. A plausible improvement is to consider that each
electron moves not only in the central field of the nucleus but also in a average central field
produced by the other electron. Thus the apparent net effect of each electron on the motion of the
other is to screen the charge of the nucleus by a certain amount. The energy of the atom in the
ground state may then be written as
E = 2(Z - S)2Eh
where Eh = -13,6eV (the energy for hydrogenlike motion) and S is the screening constant, which for
the ground state of helium must have the value of 0,32 to agree with the observed value of Ehe . That
is, the screening effect of each electron on the other is equivalent to about one-third of the electronic
charge.

As an aid, let us label the electrons 1 and 2. Since in our first approximation we assumed that the
electrons moved independently, the probability of finding electron 1 at a given position and at the
same time finding electron 2 at another given position is the product of the probability distribution
for each electron, because the two events are uncorrelated; that is, Patom=P(1)P(2). Therefore we
conclude that in the independent-particle model the wave function of the atom should be the product
of the wave functions for each electron. If we designate the orbital quantum numbers n, l, ml, of
electron 1 by a and the quantum numbers of electron 2 by b, we must then write:
Eq 4.3
resulting in a probability distribution
Eq. 4.4

Due to the motion of the electrons, the average central field that one electron produces on the other
deviates from the 1/r coulomb field produced by the nucleus. This obviously requires a slight
modification of the wave functions “qsi”1 and “qsi”2, which are no longer identical to the
hydrogenlike wave functions. The charge affects the radial part Rnl but not the part Ylm1 of the
wave function because the resultant force on each electron is still a central force. Using appropriate
mathematical techniques, we can optimize the electron wave function, and so obtain the energy
levels if the atom with relatively good accuracy.
However, even if the functions appearing in eq. 4.3 are so optimized, this expression for the wave
function of the atom cannot be correct. Wave function 4.3 says that electron 1 is in state a and
electron 2 is in state b. But the wave function 4.5 corresponding to electron 2 in state a and electron
1 in state b, must represent a state of the same energy as the wave function of Eq. 4.3 and should
describe the state of the atom just as well Eq. 4.3; The fact that the wave functions given by Eqs. 4.3
and 4.5 correspond to the same energy is called exchange degeneracy.
Now, electrons are identical and indistinguishable, and the most we can say is that the wave
function “qsi”atom be such that |”qsi”|square (whith gives the probability distribution of both
electrons) be symmetric with respect to the two electrons, in such a way that both electrons play the
same role. Neither the atomic wave function given by eq. 4.3 nor the given by eq. 4.5 meets this
requirement. But we may obtain an adequate atomic wave function ( incorporating the fact that the
electrons are indistinguishable) by making appropriate linear combinations of eqs. 4.3 and 4.5,
which happen to be the functions.
Eq 4.6