Exchange Stabilization and the Variation

of Ionization Energy in the p and dn Series

Antony B. Blake
University of Hull, Hull. England HU6 7RX
The way in which ionization energies vary within a series
of consecutive elements helps us t o understand a number of
trends in the stabilities of compounds and the oxidation-
reduction behavior of ions. This article is concerned with two
types of ionizations that are of special importance t o chemists,
namelv. the Drocesses D" - pm-I and dn - dn-l. The first
.. .
is pertinent to the chemistry of the main-group elements from
Group I11 onward, and the second is pertinent to that of the
transition elements in oxidation states +2 and above (pro-
vided n > Oi. Our main DurDose is to clarify current textbook ~~~
. .
interpretations of the peculiar decrease in ionization energy
followine comnletion of a half-filled D or d shell.'
The &r e Shows the first ionizatibn energies of the atoms
B to Ne (electron configurations ls22s22pn, n = 1 to 6), and
the energies required to remove an electron from the gaseous
ions Sc2+ to Zn2+ ([Ar13dn, n = 1 to lo), plotted against atomic
number. In hoth cases we observe a tendency for the energy
to increase with increasing atomic numher, but with a distinct
drop in ionization energy on going from the atom or ion with
a half-filled shell (p5d5) to the next one in the series. Thus,
the energy of the process M2+@) - M3+(g) + e - ( g) increases
fairly steadily from Sc to Mn, and again from Fe to Zn, but the
second approximately linear portion is shifted downward by
about 500 kJ mol-' from an extrapolation of the first. This
shift t o lower energies has some familiar chemical conse-
quences, for example, the instability of MnC13 compared with
FeCln and the fact that CoF? is not much more oxidizing than
M~F;.
It is not surprising that most textbooks of inorganic
chemistry give some discussion of these effects, and of their
origins in terms of atomic structure. Although the overall
rising tendency is easily explained hy the progressive increase
in the effective nuclear charge experienced hy the electrons,
it is not so easv t o give a simple exulanation of the decrease
following the half-Filled sheli. ~ wd a ~ p a r e n t l y different ex-
nlanations are commonlv offered. Many authors point out that
In a more than half-filleh shell, at least one orhital is occupied
by two electrons, and these electrons should experience a
greater net repulsion than those that have an orbital t o
themselves, since sharing an orhital implies that the two
electrons in it are constrained, to some extent, t o occupy the
same region of space. This explanation is simple and obvious
and is accepted readily by most students. On the other hand,
some more advanced books discuss the problem in terms of
the seemingly different and more mysterious concept of "ex-
change energy": electrons with parallel spins tend to keep
anart. in conseauence of the Pauli principle; thus, the average
repul&m herwc~n t w, r k t r t ~n . in ~ I I I ' I V W ~ ~ d, i t ai . ia Ivy. ii
their wi~i; ;ir(, w~rdllel t hm ii thc,v :ire op~,u+~l, the Liierence
arising from the presence of a so:called"exchange integral."
The first five electrons to enter the d shell go in with parallel
spins, thereby taking maximum advantage of the exchange
stabilization; but the sixth and subsequent electrons must
have the opposite spin direction, and although they still
achieve minimum repulsion among themselves, their repulsion
with the first five is not reduced hy the exchange effect, as it
would have been had they been able to go in with the same
spin direction as the first five. The two interpretations-extra
repulsion from double occupancy of orbitals, and extra re-
"
Fe"
{~r l 3d"- l ~r l 3d"~'
First ionization energies of the atoms B to Ne (electron configurations ls22s22p")
( 18) and of the divaient ions ScZ+ to Zn2+ (electron configurationr [ArISd")
(19).
pulsion due to loss of exchange stabilization with the first
half-shell-are distinct, at least superficially, and hoth seem
physically r ea~onabl e. ~ The question is "Which effect is the
more important, and which should we teach?"
In 1111; article we qhall l c ~ ~ k . a t tht v:ir~,itic,n~ i n ionimti~m
r~t err\ . oredicted in rht. 11" i u~d r l n series, anrl lr\. t o i nl i t ~ I I C I I I
intothk "classical" or ~oul ombi c repulsion energy and the
quantnm-mechanical exchange correction. We shall see t hat
the drop at the half-filled shell is due mainly to the exchange
effect, though with quite asuhstantial contribution from the
douhle-occupancy effect. Before embarking on the analysis,
however, we first outline a simple method by which ground-
state electron repulsion energies can he calculated, so as t o
make plain the significance of some concepts that we use
later.
'The discussion that follows is based on certain simplifying as-
sumptions, of which the most important is the neglect of spin-orbit
coupling. Although this approximation is valid for our purposes far
the lighter elements, including those of the 3d and 4d series, the
conclusions reached may not be correct far heavier elements where
spin-orbit coupling is strong. Charge correlation effects are also ne-
glected, since these are expected to be relatively unimportant in the
outer shells of many-electron atoms.
21t should perhaps be mentioned that anumber of textbooks offer
neither of the above explanations but refer instead to a supposed
"special stability" of half-filled shells. This mythical concept has been
admirably demolished (along with the "special stability" sometimes
attributed to filled shells) in a recent article by B. J. Duke ( I ) .
Volume 58 Number 5 May 1981 393
Electron-Repulsion Energies
We are interested in atoms or ions in which the outer elec-
trons are in a partly or completely filled p or d shell, and all
the other electrons are in filled shells (s2, p% etc.) which, to-
eether with t he nucleus. constitute the oositivelv charged
"ore" of the atom and remain essentially Lndisturbed in'the
ionization process. Each of the outer electrons can be assigned
a "private" energy, 11, which is the sum of its average kinetic
energy and the average (negative) energy of its electrostatic
interaction with the core, &d on top of this, the outer elec-
trons have a collective repulsion energy, E,,,, due to all the
electrostatic revulsions between them: When an electron is
removed from an atom with outer shell pn, the energy input
is given by
and if the repulsion energies are those for the ground states,
El is the ionbatinm enerq. lporinp; ( 1 for the present , ~ur first
task i.. to calrulat~ EICP iur 11 = 2, 3, . . .. 6. \\.esh:lll then do the
same for d".
To illustrate how this isdone, we take the configurationp2.
An electron in a p orhital can he in any one of six states (mi
= 1 , O, or -1, with m. = +%or -%), and there are therefore
15 possible ways of arranging two electrons in the samep shell.
(Remember that the two electrons cannot simultaneouslv
occupy the same state. The numher of ways of choosing twb
states from 6 is 15.) If we use boxes to represent the orbitals
and an arrow for thespin direction (up for rn, = +%,down for
-%), one such arrangement is as follows:
In using thequnlitum nun~hers I and rn, for a single electron,
we rwall that I wlls us the maenitude of the electron's orbital
-
angular momentum (1 = 0 for an s orhital, 1 for a p , 2 for a d ,
etc.) while m, gives the value of its vrojection (angular mo-
. ..
mentum being a vector quantity) aldngthe z axis. Similarly,
for an atom in a particular state there will be a total orbital
angular momentum due to all the electrons, to which we assign
the quantum number I,, and a definite projection of this in the
r direction, given by ML, which can take any of the 2L + 1
integer values from -L to +L. MI. is equal t o the sum of the
rn, values of the individual electrons. We shall also have atotal
spin quantum number S , the z-component, Ms , of which can
take any of the 2 s + 1 values from -S to +S, Ms being equal
to the sum of the rn, values. (S may be an integer or half-in-
teger.) Filled shells make zero contribution t o L and S.
It can he proved that as long as the only forces acting on the
electrons are the electrostatic attractions and repulsions
within the atom, each many-electron wavef~~nction that
satisfies the Schrodinyer equation for the atom and is a m-
sistmt with the indistinguishability of electrons must corre-
spond todefinite valuesd'L and 3 t'urther,all of the r?L +
1 1 ( 2 + 1) staws (wavefunctionc) with a particular value of
I, and S will hnve the samc energy ( i e. will he "degeneratt:").
Thr energy level correspmd~ng to such a set of degenerate
state. is called a "term" t dt he configuration, and is given a
svml~ol in the form 2sv11.. where the value of L is indicated
cbnventionally by a letter rather than a number, using
S.P.D.F.G.. . . forL =0.1.2.3.4.. . . . T h e t e r ms o f ~ ~ a r e V.
. . . . . . . . .
ID, and LS, and their derivation is a standard eiercise fo;
students of atomic structure. The lowest-energy term is 3P,
-.
as predicted hy Hund's rules.
If we write out some of the possible "arrow-in-hox" di-
agrams for p2 with their MI, and Ms values and list them
against t he terms t o which they could belong, as in Table 1,
we see that certain combinations of MI. and Ms can arise from
only one diagram, whereas others can arise from two or three.
Table 1. Some of the Fineen Possible Ways of Assigning m, and
m. Values to Two Electrons in the p Shell, with the Resulting ML
and M, Values, the Terms to Which They Can Belong, and the
ReDuision Eneraies of the Sinale-Determinant States
Possible Repulsion
M & terms enerav'
1 3P 41, 0) -
N1. 0) =
Fo - 5F2
1 ' P dl,-1)-
41,-1) =
FO - 5F1
1 'P @,-I)-
NO,-1) =
Fo - 5F2
0 3P, ' D,
' S
The box diamams actuallv reoresent wavefunctions of a rather
special type',namely, funitions ill which we can say definitely
that a oarticular ~rbi t i l l IS wcuvic~d and that the electron in
it has a particular spin directi'n. For example, the first di-
agram in Table 1 (with ML = 1, Ms = 1) represents t he
wavefunction
" -
Here, the numbers 1 and 2 in parentheses label the two elec-
trons, po stands for the orhital with rnr = 0, and the + sign
indicates that rn, = +%. Notice that * obviously describes a
state of the atom in which the orbitals po and pl each contain
an electron: however, because of the form of 'P. we cannot say
whirh electrun occupies which orbital, and this inahility fi&
in with the tact that an individual electron rannor bc disrin-
guished from any other electron. Notice also that if we inter-
change the electrons, by switching the labels 1 and 2, the sign
of *-is reversed. This property is also one that all ~ o mp l ~ t e
many-electron wavefunctions must possess: the known
vrooerties of svstems of electrons can he satisfactorilv ex-
. .
plained only if it is assumed t hat their wavefunctions (in-
cludine snin) must alwavs be antisvmmetric. i.e. change sien
.. . .. -
whenever two electronc are interchanged. The antisymmetr).
reuuiremenr is actuallv a generalized form of the Pauli ~ r i n -
--r---
An interestina orovertv of anv antisvmmetric wavefunction
that can be represented by a single box diagram is that it can
he written as a determinant of one-electron states, i n which
electron labels vary along the rows and orbital-plns-spin
designations vary down the columns (or uice-uersa). Thus *
is the determinant"
3Similarly, an antisymmetric three-electron function would have
the form
(where a, b, c include spin designations), and this is the determi-
nant
abbreviated as label.
394 Journal of Chemical Education
".
determinants ensure that they are always antisymmetric and
satisfv the Pauli exclusion principle.
NU;, the combination Mi, = ~, - Ms = 1 must belong to the
3P term of p2 ( L = 1, S = I ) , and as we have seen, this com-
bination can arise from only one box diagram. Hence the
corresponding wavefunction ' U3P;l, l) can be written as a
single Slater determinant, eqn. (3). On the other hand, two
different determinantal wavefunctions with ML = 1, MS = O
can be constructed (corresponding to the two box diagrams
shown in Table l ) , and neither of these determinants by itself
is a proper wavefunction of p2. Therefore, the wavefunction
'P("P;1,0) cannot be written as a single determinant but will
be some combination of these two determinantal functions,
and the same is true of 'P(lD;l,O). Similarly, 'P(T;O,O),
'P(lD;O,O), and 'P('S;O,O) are combinations of three Slater
determinants. It is often quite hard to determine the coeffi-
cients in such combinations.
We shall now see that the repulsion energy in a state that
can be written as a single Slater determinant is very easy to
calculate ( 2 4 ) . For a state of the atom with wavefunction T,
the repulsion energy is given by the integral
pP*H,*,$d7
in which
H,,, = ~(e214arorp, )
where r,, is the distance between the electrons labelledp and
o. and the sum is over all nairs of electrons. Although this is
. , -
a multiple integral over all space and spin for all of the elec-
trons, it can be shown to reduce to a combination of two-
electron integrals. For most states the result is still quite
comnlicated. However, for asingle-determinant state (i.e. one
corrksponding t o a single box diagram) it is given by simply
adding a term Ji, for each pair of electrons in the outer shell,
and substracting a term Kj, for each pair that have parallel
snins, the integrals J and K beina defined as follows:
. . -
J;, = S$i*(l)dj*(2)(eV4a~~r12)$,(1)$j~2)dild (q)
Kij = S$i*(I)$,*(2)(e2/4aror~%)9,(2)9,~l)d~~d~~
where d; and d; are the orbital wavefunctions of the two
, .
, ,
electrons. The J s , which are known as Coulomb integrals,
have a simnle nhvsical internretation: J;; is the average enerm
. . . - ...
of repulsion hetween two electrons whose motions conform
to the nrobabilitv densitv functions Id; 1 and Id; 1 2 , or (looking
, . , , . , , .
at it in another way) the energy of interaction between two
clouds of negative charge 14; I2e and I@j1 2e. (If i = j , this is the
classical "self-energy" of the charge cloud.) The Ks are called
exchange integrals, and if 4j and @, are real functions, Kij can
be identified with the energy of repulsion between two su-
perimposed "overlap" probability densities 4i4, (the "self-
energy" of the charge distribution @i@,e). Knowing the orbital
wavefunctions mi , we can in principle calculate these integrals
once and for all. Since J and K are always positive (at least,
for single atoms or ions), it follows that the more pairs of
electrons have parallel spins, the lower will be the energy. This
is "exchange stabilization." The reason that it arises only for
parallel-spin electron pairs is closely linked with the an-
tisymmetry requirement, and a very clear explanation can be
found, for example, in Linnett's little book "Wave Mechanics
and Valency" (5).
The repulsion energies of some states of p2 that can be
written as single Slater determinants are given in Table 1 in
terms of the integrals J(mi,mr') and K(mi,ml') for p or-
bitals.
We now proceed to calculate the Coulomb and exchange
contrihutions to the repulsion energies of all the p" and d"
ground terms. This determination is quite straightforward
because, in any configuration, the wavefunction with the
largest possible number of unpaired spins, and the highest ML
consistent with this, will always he a single-determinant
function (since there is only one hox diagram that satisfies
these conditions), and will also belong t o the ground term
(Hund's rules).
Energies of p" Ground Terms
Using the ml Orbitals
The "ml" orbitals usually used in calculations on free atoms
or ions are products of a radial function, R( r ) , and an angular
function of the polar coordinates (H,@), the latter generally
being a complex function. The two-electron integrals
J(ml,mr') and K(mi,ml') in eqns. (4) can be reduced, by in-
tegrating over the H and @ coordinates of each electron, to
linear combinations of integrals of the radial function alone,
known as Slater-Condon integrals, of which for p electrons
there are two. denoted F o and F?. Table 2 gives the values of
the J s and KS in terms of Fo and F2(6), and in Table 3 we
have listed the ground term of each confiauration P", with a
box diagram for-one of its component states and the Coulomb
and exchange contributions to its energy. [For example, for
the p5 state shown, we have 2J(-1,O) + 2J(-1, l) + 4J(0,1)
+ J(0,O) + J ( l , l ) = 1OFo - 5Fa, and -K(-1,O) - K(-1,l) -
2K(0,1) = -15F2.1
Using Equivalent Orbitals
A disadvantage of the orbitals D-,. DO. and DT is that they
. .. . .. . .
implicitly s i ngl ekt a particular direction (the z axis), so that
D" has a different soatial form from D-I and DI . (Its nodal
. -
surface is the ny plane, whereas fur p l l and pi t he z axis is a
node.) However, any set of three independent linear combi-
nations of these wavefunctions is equally acceptable from the
quantum-mechanical point of view, and for pictorial purposes
the orbitals p,, p,, and p,, defined by eqns. (5), are more
convenient, because they are real functions and are spatially
Table 2. Coulomb and Exchange Integrals for the Orbitals p,, PO,
and p-,
Table 3. Ground-State Electron-Repulsion Energies of p"
Configurations, Calculated by the Use of the Orbitals p,,po, and
D-. and Analvsis of Eneraies for r," - 0"-'
p" ground Coulomb Exchange
term. and energy energy
typical slate ZJ - 2 K Em,
Change Change
in ZJ in - 2 K Change in Em,
Volume 58 Number 5 May 1981 395
PZ = (PI + P - J I J ~
P, = (PI - p- dl i J 2
P. = PO ( 5)
equivalent. Students are familiar with these orbitals, and
Howald and Muharak (7) have pointed out that they can be
used for calculating electron repulsion energies just as easily
as p-I, po, and p l can. Their spatial equivalence also makes
them very convenient for our purpose, because it means that
they give only two distinct repulsions: the one between two
electrons in the same orhital, and the one between electrons
in any two different orbitals (Tahle 4). We shall use J,,,, t o
Table 4. Coulomb and Exchange Integrals tor the Orbitals p., p,,
and PZ
Table 5. Some Assignments of Orbltals and Spins to Two
Electrons in the Orbitals p,, p,, and p., wlth the Resulting
Octahedral Symmetry Types and Mr Values, and the Repulslon
Energies at the Single-Determinant States
Possible
M1 terms Regulsion energy
Table 6. Ground-State Electron Repulsion Energies ot p"
Configurations, Calculated by the Use of the Orbitals p., pr, and
p, and Analysis of Energies for p" - p"-'
p" ground Coulomb Exchange
term, and energy energy
typical state ZJ - ZK Em
Dt 2 . r ,+ 0 0 0
. . I
9 3T7 ~ ~ . + p y t ~ Fa- 2F2 -3F2 Fo - 5 Fz
d 4A, I P ~ + P ~ + P ~ + ~ 3F0- 6F2 -SF, 3Fa- 15Fz
$ 3T7 / P ~ ~ P ~ ~ P ~ ~ ~ 6Fa- 6F2 -SFz 6Fo - 15F2
d T; 1 P , ~ P ~ ~ P ~ ~ 1 10F0- 8F2 -12F2 10F0 - 20F2
P' ' A, lpx2p?pZ21 15F0 - 12F2 1 8 F 2 15F0 - 30Fz
Change in ZJ Change in - 2 K Change in E,.,
Note: J = A,, = Fo - 2F2: K = 3F2
Table 7. Coulomb and Exchange Integrals for the "cubic" d
nrhitals
so, cc. E . 77. rc
A+48+3C
I
A+4B+ C C
@. 07
A+2B+ C B+ C
ft, 67. 7. 7 c E A- 2B+ C 3B+ C
flc flt A- 4B+ C 4B+ C
stand for J(xx), etc., Jd,ff fur J(xy), etc., and K for K(xy),
etc.
Since these orbitals do not all have definite values of ml, the
single-determinant wavefunctions constructed from them
cannot usually be assigned ML values. However, if in imagi-
nation we impose on the atom an octahedral "crystal field"
(which can be as weak as we like), we can classify the free-atom
terms having L = 0, 1, 2, etc. by the labels used in octahedral
symmetry, according to the well-known correlation S - A1,
P - TI, D - E + Tz, and so on. A little group theory (8) also
enables us to find to which symmetry type each singIe.de.
terminant wavefunction (or box diagram) belongs. As in the
L, ML case, it turns out that at least one box diagram with the
maximum numher of unpaired spins is of a unique symmetry
type and thus can contribute to only one state ofp". For the
p2 case, illustrated in Table 5, the components of the 3T1 term
are single-determinant functions; therefore, we can calculate
the repulsion energy of this term (which is really the 3P term)
by the ZJ - 2 K rule, using now the J a n d K integrals in Tahle
4. (The latter are derived readily from Tahle 2 by use of eqns.
5.) The results for all the p n ground terms are listed in Table
6.
The Ionization Energies
Let us now look at the changes in the ionization energy, eqn.
(I), as we go from one p n configuration to another. We must
hear in mind, of course, that U, and also F o and F2, are not
nuclear charge increases. Indeed, the overall rising trend of
the ionization energies is due mainly t o the increase in -U
with increasine nuclear charge. andFn and Fq also increase
nuclear chargk when an electron is removed. However, the
variations seem t o he smooth enoueh to he nedected in a
semi-quantitative discussion of the "&upn after the half-filled
shell. and we shall proceed as if Fo and F? were constants.
WL look first at the results obtained uBing p,, p,, and p,
(Table 6). If there were an unlimited supply of vacant orbitals,
then each time we added an electron tip" t o givepn+', the
number of electron pairs would increase by n and the repul-
sion energy would increase by n(Jdiff - K) , since all the elec-
trons would he in separate orbitals with parallel spins. The
effect of this would merelv be t o make the steadv increase in
ionization energy slightly Lss steep. In fact, this picture is true
onlv for the first three electrons: once the shell is half filled.
we must modify the contribution of each subsequent electron
to Erep by an extra J,,,, - Jdiff = 6F2, because it has t o share
an orbital, and by an extra 3K = 9F2 representing loss of ex-
change stahilization, because its spin is opposite to that of the
first three electrons. The resulting 15Fz of "extra" repulsion
energy, which will apply to each of the electrons in the second
half shell, can be identified with the anomalous downward
shift in ionization energy, and we see that 215 of it arises from
the increased Coulomhic repulsion associated with sharing
an orbital, and 315 from the loss of exchange stabilization due
t o the necessarv reversal of spin.
It is instructive to repeat this analysis using the orhitalsp-1,
D". and D, (Table 3). The situation now is complicated
. ".
slightly byt he fact that the repulsion between two eiectrons
depends on which orbitals they occupy, but we can proceed
by calculating the auerage J or K and examining the-energy
incrementsin terms of these averages. Thus we haveJ,,, =
Fo + 2Fz, Jdi i f = FO - Fz, and K = 4Fz. (Note that these av-
erage values differ from those for p,, p,, and p,.) We again
find an "extra" repulsion energy 15F2 in the segnd half shell,
but this is now made up, on average, of J,,, - Jm = 3Fz due
to double occupancy and 3K = 12Fz due to loss of exchange
stahilization. i.e. and % of the total, respectively. The dif-
ference between this result and that ohtained withp,, p,, and
p, is a useful reminder that the distinction between "Cou-
396 Journal of Chemical Education
lomhic" and "exchange" components of the net repulsion
energy is to some exteGt an arbitrary one: the extent to which
the exchange "correction" is necessary will vary with the or-
bital wavef;nctions used in the calc&tion. Still, it seems
reasonable to say that the anomaly in the ionization energies
of the elements B to Ne is due mainly to the effects of
quantum-mechanical exchange. In other words, it is a conse-
quence of the Pauli principle.
Energies of d" Ground Terms
The electron-repulsion energies of d orbitals depend on
three radial integrals, and it is customary to use the Racah
parameters, defined as A = Fa - 49F4, B = F2 - 5F4, and C
= 35F4. As in the pn case, the calculation is easier and more
physically satisfying if real orhitals are used, and we shall use
the well-known "cubic" orhitals d, ~, d,n -y 2, dxy, dyi, and d,,.
To simplify the notation, we shall relabel them as 0, e, 5; f , and
7, respectively. Their J and K integrals are given in Table 7
191
\-,.
The reader will notice that even with these real orhitals we
have to consider five types of interactions, compared with only
two for the real p orhitals. (If the complex d orbitals with mi
= 0, f 1, f 2 are used, there are nine distinct interactions.) It
appears t o he impossible to find a set of d orhitals for which
all int.ernct,ions hetween electrons in different orbitals are ------ ~
equal, as we can in the p case. (One can liken this circumstance
to the fact that in three dimensions it is impossible to arrange
five points so that all ten interconnections are equivalent.) It
is true that sets of spatially equivalent d orhitals exist, namely,
the pentagonal-prismatic orbitals of Powell (10) and Pauling
and co-workers ( I l ) , but even with these there are still three
types of interactions, and moreover, these functions do not
seem to give single-determinant ground states, which are es-
sential for the simple approach we wish t o use. So we have to
content ourselves with the familiar "cubic" d orbitals.
The n-electron wavefunctions are again classified according
to their symmetry properties in an imaginary octahedral en-
vironment. For most configurations the free-ion ground term
splits into two or three "crystal-field" terms, but in all cases
at least one component is a single-determinant function of
unique symmetry type (see Appendix). The repulsion energies
can thus be obtained as hefore, and in Table 8 we list the
"Coulomhic" and "exchange" contributions, and the analysis
of d" - d*-' .
From Table 7 , we have J,,,, = A + 4 8 t 3C,Jdiff = A - B
+ C, and K = 2.5B + C. On the average, therefore, we expect
addition of each electron in the second half-shell t o involve
an extra repulsion of J,,,, _Jdl f f = 5B + 2C due t o double
occupancy, plus an extra 5K = 12.58 t 5C due t o loss of
exchange stahilization with the five electrons of the first half-
shell. In other words, the downward shift in ionization energy
amounts to 17.5B + 7C, of which 2/7 arises from the increase
in Coulomhic repulsion associated with sharing an orbital, and
517 from loss of exchange stabilization.
" Small deviations from the "average" behavior are inevitable
because of the inequivalence of the five orhitals. The d2, d3,
d7, and d8 configurations can achieve arrangements with
especially low repulsion energy; for example, the second
-~~~~ ~
than the~&erage'per eiectron pair. This <xtra'stability can be
maintained (hv means of a different arrangement) with three
-
electrons hut is cancelled out when the fourth is added. A
similar situation naturally arises in the second half-shell. (In
the lanthanide series, these deviations give rise to the chem-
ically significant "quarter and three-quarter shell effect," as
discussed by Johnson (13). )
The d" case can be treated also in terms of mi orhitals, and
it is found that, of the 17.58 + 7C extra repulsion, is due to
orhital sharing and 4/5 to loss of exchange. As in the p" case,
the wav in which we annortion resoonsibilitv for this extra ~ ~
~~, . .
repulsion thus depends to some extent on the type of orhitals
we use. hut aeain it seems that most of it can he attributed t o
the exchange effect, and only about a quarter t o the sharing
of orbitals.
The advantages of using a set of equivalent orbitals in mo-
lecular calculations were pointed out many years ago by
Lennard-Jones and Pople (14). As they observed,
The respective values of the Coulomb and exchange contributions
depend on the form chosen for the orhitals. I t turns out t hat the en-
change oart is small when eauivalent orhitals are used. and the Cou-
bitals.
They note, however, that the reduction in exchange energy
In atoms, it seems that the use of equivalent orhitals in re-
Table 8. Ground-state Electron-Repulsion Energies of d" Configurations and Analysis of Energies tor d" - d"-'
a" ground term Typical stales 2 J - 2 K Em,
d' 'D('E+ 'T2) at r 0 0 0
B3F( 3A2+ 3 T < t 3T2) I/)++ I o t c l + + A- 4 8 t C - 48- C A- 88
a4F( ' A, C 4T,+ 4T2) It+?+!? I t ?++I+ + 3A- 6BC 3 6 -95- 3C 3A - 158
d SD(5E+ 'TA If+[+?+? I t V 0 1 6A- 6B+ 6C -158- 6C 8A - 218
8 'S('A1) l J +c +t +?+pl 10A - 108+ 1OC -258- 1OC 10A - 358
8 5 D( 5 E+ 'T2) etc 15A - 10B+ 17C 2 5 8 - 1OC i5A - 358 t 7C
d7'F('A2+'TVf 'Tzl 21A- 148+25C -298- 11C 21A- 4 3 Bt 14C
d8 lFi3Ag + 3T3 + 3T9) 7RA - 168+ 341: -348- 13C 28A- SOB+ 21C
, -. .. ~- ~ -
2~i2E+ 2 ~ 2 ) 36A - 165 C 44C -408- 18C 36A - 568+ 28C
d'O ' S(' A<) 45A - 2 0 8 t 55C -508 - 20C 45A - 708+ 35C
Change in Z J Change in - 2 K Change in E,,,
-
d 2 - d 2- 38 - K- - 1.58 I- K - 4.58
d3 - d2
2' -2l5 2"- K)
d4 - d3 3_J+ 38 -3K+ 1.58 3( J- X) + 4.58
d5 - d4 4!
- 4E 4(J- X )
d8 - d5 SJ+ 58+ 2C -51(+ 12. 581 5C 5(J-K)+ A
d7 - de s>+ 28+ 2 c - 6_Kt 118 + 5 C 6(J- M t A - 4.58
ds - d' 7J+ 58+ 2C -75+ 12.58 t 5 c 7( j - - + A
d9 + ds G+ ~ B+ Z G -8K+ 14 8 C 5C
a(?- K) + A + 4. 58
8" -S 9 J t 58+ 2 6 - 9K+ 12.5B+ 5C s ( J - %+A
N ~ ~ ~ : J = J ~ ~ ~ = A - ~ + c : K = ~ . ~ B + c ; A = ~ ~ s B + ~ c .
or thedivalent ions of the first transition series. C-45- 30-50 kJ mol-' (14.
Volume 58 Number 5 May 1981 397
pulsion-energy calculations also serves t o minimize t he ex-
change corrections, as well as making the physical effect easier
t o visualize. Nevertheless, as far as t he trend in ionization
energy in a series of elements is concerned, the exchange effect
clearly emerges as dominant.
Conclusions
(1) The decrease i n p n - pn-' or d n - dn-' ground-state
ionization energy following completion of the first half-shell
is due mainly t o extra interelectronic repulsion resulting from
the fact t hat t he electrons of t he second half-shell have op-
posite spins t o those of t he first (i.e., t o t he absence of "ex-
change stabilization" with respect t o repulsions between t he
first and second half shells). This effect, which can be regarded
as a correction t o t he ~ u r e l v electrostatic model by incoruo-
t o extra repulsion arising directly from t he fact t hat t he
electrons of t he second half-shell have t o share orbitals with
those of t he first.
(2) The relative importance of these two factors depends
on the choice of orbitals used t o construct t he many-electron
wavefunctions: the use of orbitals t hat are, as far as possible,
spatially equivalent (e.g. p,, p,, and pJ maximizes t he con-
tribution from orbital sharing, hut the exchange contribution
remains dominant.
Acknowledgment
This article has henefitted greatly from discussions with Dr.
Peter G. Nelson, for whose perceptive criticism and many
constructive suggestions I am most grateful. Dr. Nelson made
a partial study of t he d n - dn-' case several years ago ( 15) ,
the conclusions of which have been published by Johnson (16).
I am also grateful t o Dr. David E. Webster for very helpful
comments on t he manuscript.
Appendix
d12+2, ete. We wish to find a single-determinant component of 3F,
and since the spin part will be symmetric when the number of parallel
spins is a maximum, we need an antisymmetric spatial function. In
cubic symmetry the orbitals transform according to the standard ir-
reducible representations r z and e , and their antisymmetrized direct
products span the following irreducible representations: e2 - A?; ts2
-TI; tze and etz - TI + T?. Since TI occurs twice, its components
will in general be mixtures of tz2 and t2e products. Az arises only from
the product Oc, and hence IB+c+l PA21 is a single-determinant com-
ponent of 3F.
A more complete analysis can be made by inspecting the
"Clebsch-Gordan" coefficients connecting products of particular
one-electron functions with the two-electron states of appropriate
symmetry that can be constructed from them. For real p and d ar-
bitals in cubicsymmetry theseare given by Griffith (17),Table A20.
For T? we find that the [ and q components are mixtures of products,
but the [component arises only as the product Or, and lfl+Pl PT2)
is therefore the only other single-determinant component of 3F that
can be constructed from the real d orbitals. We can also extend these
results to d3 by noting that the orbital symmetry behavior arising from
two empty orbitals will be similar to that of d2. The rest of the results
follow.
error or by s variational procedure, a determinantal function that
gives the same energyas that obtained in the ML scheme
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398 Journal of Chemical Education