Before discussing in detail, the ground state and various excited states of two electron

atoms, we shall develop in this section a simple approach which yields a qualitative
understanding of the main features of their and which will also pave the way for our
study of many- electron atoms in Chapter 7.
We begin by rewriting the basic Hamiltonian [6.2] as
𝐻 = 𝐻0 + 𝐻′ [6.23]
where we choose our zero-order, 'unperturbed' Hamiltonian to be

[6.24]
while the 'perturbation'
[6.25]

is the electron—electron interaction. We remark from [6.24] that Ho is just the sum of two
hydrogenic Hamiltonians, namely
[6.26]

Where

[6.27]

In what follows we shall denote by Ent the energy eigenvalues and by PHI the corresponding
normalized eigenfunctions of the hydrogenic Hamiltonian [6.27]. Thus
[6.28]
with

[6.29]
Let us for the moment neglect the electron—electron repulsion term [6.25]. The
Schrödinger equation [6.3] for the spatial part of the two-electron WOW function then
reduces to the 'zero-order' equation
[6.30]
Using [6.26] - [6.29], we see that this equation is separable and that eigenfunctions of
[6.30] can be written in the form of products of hydrogenic wave functions. In particular,
for discrete states, we have

16.31]
the corresponing discrete energies being given (in a.u.) by

[6.32]
We note that the wave function
 [6.33]
which differs from [6.31] only in an exchange of the electron labels, corresponds to the
same energy This particular case of degeneracy with respect to exchange of electron labels
is called exchange degeneracy. According to the discussion of Section 6.2 the exact spatial
wave functions of two-electron atoms must be either symmetric or antisymmetric with
respect to the interchange of the coordinates rl and rz of the two electrons. The proper
(zero-order) spatial wave functions of our simple independent-particle model must
therefore be the symmetric (+) and antisymmetric (—) linear combinations

16.34]

where the factor 2-1/2 guarantees that the functions are normalized. The functions are
therefore approximations to the para wave functions, while the functions are
approximations to the ortho wave functions. We see that the total orbital quantum number
L can take the values L — Il — I, … Il + 12, the possible values of the quantum number
ML being ML —L, …, +L. We also remark that in our crude model the two states Psi
correspond to the same energy Ena. We shall see below that the electron - electron
repulsion term l/r2 removes this degeneracy.
An exception to [6.34] occurs for the case of the ground state, where both electrons are
in the 1s state (that is, = — 12 = O, ml = "12 = O). The wave function for the ortho state
is then seen to vanish, in agreement with the original formulation of the Pauli principle,
according to which two electrons cannot be exactly in the same state. Indeed, the spatial
quantum numbers for both electrons having the same values n = l, l = O and m = 0, the
spin quantum of the two electrons must be different, so that the two electrons must have
antiparallel spin, and only the singlet (para) state is allowed. It is interesting to note that
historically the argument was made the other way around, the experimental absence of
the ground state triplet level of helium having provided key evidence that led Pauli to the
discovery of the exclusion principle.
The normalized zero-order spatial wave function for the ground state of two-electron
atoms is therefore given by the simple symmetric (para) wave function

[6.35]
where the subscript indicates that we are dealing with the ground state, and we have used
the fact that the ground state wave function of the hydrogenic Hamiltonian [6.27] is
Z3 1/2
= Vis(ri) ¯ e 16.36]

The ground state energy corresponding to [6.35] is (see [6.32])

[6.37]

Thus, for helium (Z — 2) we find from [6.37] that ESO) = —4 a.u. — 108.8 eV), which
corresponds to an ionization potential 1(0) = 2 a.u. 54.4 eV). The experimental values
are E8XP —2.90 a.u. -79.0 eV) and — 0.90 a.u. (—24.6 ev). As we should expect, our
crude model gives an energy which is too low because we have neglected the repulsion
term [6.25] between the two electrons, whose effect is clearly to raise the energy levels.
It is also apparent that our simple independent particle approach should yield better
results when Z is increased, since in that case the relative importance of the neglected
term l/rn becomes-smaller. For example, in the case of the C4+ ion, corresponding to Z =
6, the approximation [6.37] yields Eo — —36 a.u. —980 eV) while the experimental
ue is EfiXP —32.4 a.u. -82 eV). On the other hand, for the negative hydrogen ion H - (Z
= l), the value I a.u. —27.2 eV) is in gross disagreement with the observed value
Eexp = -0.528 a.u. —14.4 eV).
Let us now examine the predictions of our simple model concerning excited states.
The energy spectrum corresponding to [6.32] is illustrated in Fig. 6.5(a) for the case of
helium (Z = 2). Also shown for comparison in Fig. 6.5(b) is the experimental spectrum.
We first rernark that the energy levels E corresponding to states for which both electrons
are excited (that is, nu 2 and n2 2) are higher than the ground state energy of He + ion
(Eo(He+ ) — —2 a.u. 54.4 eV) plus a free electron. The doubly excited states therefore
lie in the continuum of our simplified spectrum (see Fig. 6.5(a)). Since the repulsion term
1/r12 can only raise the unperturbed energy levels E(O) , the same property is also true
for the actual He spectrum, and in fact it holds for all other He-like ions. We shall return
at the end of this chapter to these discrete states embedded in the continuum. For the
moment, however, we focus our attention on the genuinely discrete states of two-electron
atoms, for which one of the two electrons remains in the ground state. The properly
symmetrised zero-order spatial wave functions for these states are given (see [6.34]) by

n > 2 [6.38]

and are therefore characterised by three quantum numbers (n, I, m) as in the case of one-
electron atoms. The total orbital angular momentum quantum number L is given by L = I
and the values Of ML (=m) are ML = —l,
l. The energy levels corresponding to the wave functions [6.38] namely (see
[6.32])

[6.39]

are degenerate in I and m. As out above, they also exhibit the exchange degeneracy,
according to which the para (+ ) and ortho ( levels are degenerate in the 'zero-order'
approximation [6.38]. The electron—electron repulsion term I , which is ignored in the very
simple approach leading to [6.39], will clearly raise these energy levels, as may be seen from
Fig. 6.5. As we shall show at the end Of this section, the term l/r12 is responsible for
removing the exchange degeneracy between the para and ortho states.
For the special case of the negative hydrogen ion H¯, corresponding to Z1, the repulsive
term l/r12 has an even more drastic effect on the spectrum, as Fig. 6.6 illustrates. all the
excited states [6.39] which are present in the 'unperturbed' spectrum shown in Fig. 6.6(a) are
lifted into the continuum when the electron—electron repulsion l/rn is taken into account
(see Fig. 6.6(b)). This spectacular effect of the 'perturbation' l/r12 is obviously due to the
small value (Z = l) of the nuclear charge. In what follows, when discussing the excited states
of two-electron atoms, we shall assume implicitly that we are dealing with the case Z 2.
 So far, we have used a very crude independent-particle approximation, in which the
electron—electron repulsion term 1/r12 iS completely omitted. While remaining within the
convenient framework of the independent-particle model we may improve our treatment by
splitting the basic Hamiltonian [6.2] ag
[6.40]

where

_ + V(rz) [6.41]
is the sum of the two individual Hamiltonians

+ V(rD [6.42]
and
— — — V(rz) [6.43]

In the above formulae potential which should be chosen in such a way that the effect of
A ' is small. In Chapter 7 we shall study in detail this central field approximation for many-
electron atoms, but for the moment we limit ourselves to simple qualitative considerations.
Roughly speaking, the net effect of each electron on the motion of the other one is to screen
somewhat the charge of the nucleus, so that a simple guess for V(r) is

V(r) 16.44']

where S is a 'screening constant' and the quantity Ze = Z — S may be considered as an

'effective charge'. Since the potential [6.44] is a Coulomb interaction, the corresponding
individual electron energies are given (in a.u.) by (see [6.29])

[6.45]
and are independent of the quantum numbers li and mi. Neglecting the perturbation H', the
total energy of the atom is just the sum of the individual electron energies [6.45]. In
particular, the ground state energy Eo is then given approximately (in a.u.) by

[6.46]
the corresponding spatial part of the ground state wave function being (F [6.35])
 Vo(rl, h) = e —Ze(n + "2) [6.47]
In the next section we shall use the variational method to determine the 'optimum' value of
the effective charge ze. Here we simply remark that the value Ze = 1.70 would make the
approximate expression [6.46] agree with the experimental value Eo = —2.903 a.u. of the
ground state energy of helium. Since Z = 2 in this case, the corresponding screening
constant is S = 0.30. Thus, for the ground state of helium, we see that in this simple,
‘average shielding' approximation, the screening effect of each electron on the other one is
equivalent to about one-third of the electronic charge.
A better choice for the central potential V(r) than the Coulomb form [6.44] is provided
by an expression of the same type, but in which the 'screening constant' S varies with the
distance r. Indeed, at small distances (r O), the potential acting on an electron is essentially
the Coulomb attraction —Z/r of the nucleus, while for large r (r this potential is just the
Coulomb field —(Z - l)/r due to a net charge (Z - 1), namely the nuclear charge Z screened
by the charge I) of the other electron. Thus, we expect the quantity S in [6.44] to be in fact
an increasing function of r, which takes on the values S Oatr = 0 and S = 1 atr = x. Since a
potential of the form [6.44] where S is a function of r is no longer a Coulomb the I
degeneracy which is characteristic of the Coulomb field is removed. Thus, the individual
electron energies Enl (where we have dropped the subscript i) are still degenerate with
respect to the quantum number m, but now depend on both quantum numbers n and I. The
principal quantum number n is defined as in the case of hydrogenic atoms, the number of
nodes of the radial function being n r —— n — I — I, with n = I, 2, . and 1 - 0, 1, l. Calling
unim(r) an individual electron orbital, solution of the single-particle equation

+V = EnlUnlm(r) [6.48]
we see that unlm(r) is just the product of a radial function and a spherical harmonic Yim(9,
4). It is important not to confuse the orbitals unlm(r), whose radial part depends on V(r) and
is likely to be a complicated function, with a hydrogenic function whose radial part
corresponds to the particular choice V(r) —Z/r, and which has been obtained in Chapter 3.
Let us now return to the hamiltonian (6.41]. In terms of the individual electron orbitals
unlm(r), our ne zero-order spatial wave functions, which are the properly symmetrised [6.41]
are given by

01, h) ¯ [6.49]
for the ground state and by
6.50
for the genuinely discrete excited states. If we still neglect the perturbation H’ the total
energy of the atom is just
6.51
1
and the total orbital angular momentum quantum number is L = l. The para (+) and ortho (—
) states [6.50] are still degenerate, but the degeneracy in I Lt removed. For a fixed value of n
the (algebraic) value of Enl is an increasing function of l. Indeed, electrons with a smaller
value of I are more likely to penetrate at certain times the 'centrifugal barrier' (which is
proportional to l(l+ l)/r2) and hence to feel the fully unscreened attractive Coulomb potential
—Z/r of the nucleus. We therefore expect that the energy of the atom will an increasing
function of L (=l). That this is the case may be seen from Fig. 6.2. We note that in the central
field approximation leading to [6.51] the energy of the atom is specified by the electron
configuration, that is by the values of the quantum numbers n and I of the electrons. For the
genuinely discrete states of two-electron atoms considered here, one electron remains in the
ground state (that is, with n — I and I = O) while the other, 'optically active' electron has the
quantum numbers n and l. Following the convention used in spectroscopy the values of n and
I are usually indicated by writing n as a number, and I as a letter, according to the code
described in Chapter 3 (i.e. s for I = 0, p for I = l, d for t 2, etc.). If there are k electrons having
the same values of n and l, this iB denoted as (nt)k . For example, in this notation the ground
state [6.49] is characterised by the configuration (Is)2 [also written Is2], the first excited states
[6.50] by the configurations [or Is2s], [or Is2p], and so on. It is of course understood that
when we write for example (Is)(3s) this does not mean that electron 1 (say) is in the state Is
and electron 2 in the state 3s, since we know that property symmetrised spatial wave functions
must be used in order to obtain two-electron wave functions y which are fully antisymmetric
in the space and spin coordinates of the two electrons.
From our discussion of the wave functions of one-electron atoms it is also clear that for
states of the excited electron corresponding to large value of n and I the orbitals unlm(r) are
concentrated at much larger values of r than > ground state orbital ui00(r). We may then
speak of an 'inner' (Is) electron with spatial quantum numbers (l, O, 0) which is moving in
the unscreened Coulomb field —Z/r of the nucleus, and an 'outer' electron, which moves in
the fully screened potential —(Z — I)/r. For such states of large n and I the 'zero-order'
energy levels are then given approximately (in a.u.) by

2 [6.52]
2 2 n

Apart from the addition constant —7-2 /2, we see that these energy levels are identical to
those of a hydrogenic atom of nuclear charge Z — l. This can be illustrated by drawing the
energy levels of atomic hydrogen (shifted by the amount —1/2 a.u.) next to those of helium.
We shall not pursue further here the study of the central field approximation. From the
above discussion it is clear that according to this approximation each electron moves
ind4Endently of the other one in a net central potential V(r) which represents the attraction
of the nucleus plus some average central repulsive potential due to the other electron. This
basic idea, first expressed by Hartree in 1928, will be fully developed in the next chapter. It
is also apparent from the foregoing discussion that the averaged repulsive effect of the other
electron depends on its dynamical state, so that a single potential V(r) cannot, even
approximately, account for the entire energy spectrum of the atom.
To conclude this section, we shall now give a simple, qualitative argument showing how
the exchange degeneracy is removed when the electron—electron repulsion term 1/r12 is
taken into account. Returning to the symmetrised zero—order spatial wave functions [6.38],
we first observe that the spaceantisymmetric (ortho) wave functions 1!/_!) given by [6.38]
vanish for rl = r2, so that in ortho (spin triplet) states the two electrons tend to 'keep away'
from each other and hence, on the average, have a relatively small repulsion energy. On the
other hand, the space-symmetric (para) wave functions do not vanish for r2, so that in
para (spin singlet) the two electrons may be very close at certain times and experience on
the average a stronger repulsion than in the corresponding ortho state having the same values
of the quantum numbers (n , l , m). Therefore, the electron-electron repulsion term 1/r12 is
more effective in raising the energy of the atom in the para (spin singlet) states, from which
we conclude that an ortho (triplet) State must lie lower than the corresponding para (singlet)
state having the same values of (n, I, m). That this is indeed the case may be seen for example
 in Fig. 6.2. Thus, as pointed out in Section 6.2, the Pauli exclusion principle introduces a
coupling between the space and spin variables of the electrons, which act as if they were
moving under the influence of a force whose sign depends on the relative orientation of their
spins. Such a force, which has no classical analogue, is known as an exchange force, and its
effects will be studied in detail in Section 6.6.
It is worth stressing at this that exchange forces are negligible between two electrons
which always remain far apart. Indeed, in that case the wave functions Of the two electrons
have a vanishing]y small overlap, and the two electrons may be considered as
distinguishable. An example of this situation is provided by the electrons of two hydrogen
atoms which are located at a large distance from each other. Similarly, for excited states of
two-electron atoms with high values of both n und l, the 'outer' orbital has a very small
overlap with the 'inner' (Is) orbital. The exchange force is then very small and the para and
ortho levels are nearly degenerate as may be seen from Fig. 6.2. On the other hand, for small
values of n and I (in particular for S-states) the orbitals of the two electrons overlap
significantly, and the energy difference between para (singlet) and ortho (triplet) states is
appreciable as shown in Fig. 6.2.
The results we have obtained in this section thus show that in addition to their symmetry
property (para or ortho), the spatial wave functions for the genuinely discrete states of two-
electron atoms may be characterized by the three quantum numbers n, I(=L) and
The ground state is a para state and is non-degenerate. Excluding the negative hydrogen ion
H (which has no other bound state than the ground state), the energy levels of the excited
states are degenerate with to ML ahd depend on n, on I and on S (with S O for
para states, and S = I for ortho states). The energy levels or terms may therefore be labelled
by the symbol
2S+1

where the multiplicity 2S + I takes on the values I or 3, and the code letters S, P, D, . . .
correspond to L = O, I, 2, . as we have seen in Section 6.3. Thug in this notation the
ground state is denoted by I I S and the following energy levels (by order of increasing
energy) are 2 3S, 2 I S, 2 3P, 2 1 1), and so on. In the following two sections we shall study
successively the ground state I and various excited states by using perturbation theory
and the variational method developed in Chapter 2.