Relativistic Effects on Chemical Properties

Donald R. McKelvey
Indiana University of Pennsylvania, Indiana, PA 15705

Certain anomalous chemical properties have been noted for Schrodinger equation correctly predicted the hydrogen
the heavy elements. Two classical examples are the unique spectrum and the predictions could be extended to more
properties of gold and mercury as compared to the other complicated atomic systems. But there were still problems.
members of their families. A third example is the reluctance The Schrodinger treatment by itself could not account for the
u i t h r 1)"-rtranitiw~~nct:~l, ~ i l ~ ~ lt hj ei t hi:l~c-~ jptli.ilh fine structure in the hvdroeen atom. In fact. the Bohr-Som-
uuidntim > I J I ~'I'lie
, . ~ r ~ l c r~r, ~x i~dla ~.t.utt
i ~ ~ lor
i the-t clt -
ments is two less thanthe group number. Thus, in Group IVA, - .
the most stable oxidation state of lead is f 2 , while tin exhibits Also, when the ~chrodingerequation was applied to the
stable oxidation states of both +2 and +4. This phenomenon spectra of the alkali metals, it predicted singlets where dou-
has been attributed to the so called "inert pair" effect. I shall blets are actually observed.
discuss how these and other anomalous chemical properties In 1925 George Uhlenbeck and Samuel A. Goudsmit showed
may he explained on the basis of relativistic effects. In order that the Schrodinger treatment could be made to account
to do this properly, I would like to trace the development of correctlv for the fine structure of the hydrogen spectrum and
the relativistic wave equation, the Dirac equation. starting
with the Bohr treatment of the hydrogen atom. For those
readers who are unfamiliar with the Dirac equation, I would abo& an axis through its center whiie at the same timecir-
also like to summarize some of its major consequences. culating about the nucleus. Thus, the electron would have an
angular momentum due to its spinning in addition to the an-
The Bohr Atom gular momentum which it possesses due to its circular motion
During the latter half of the 19th century it was difficult for ahbut the nucleus. Uhlenbeck and Goudsmit assigned a spin
scientists to understand why a heated gas of hydrogen atoms angular momentum of 'I& to the electron in order to explain
should emit electromagnetic radiation of only certain energies the doublets observed in the suectra of the alkali metals. It was
rather than a continuous spectrum of energies. There was no l'urll~cr:twllllit d l l l n t lht -pill :111:1lli,r ini.,tIIelitunl \c.rIc.r a.1-
theory which was adequate in explaining the hydrogen spec- cl)n,e t ~ u , ~ ~ i ~and d 1 % hc 3 l i-~ n %I
i / chad t I ithcr \ r ~ t h
t l r .xr~i~i,t
-
trum until 1913 when Bohr formulated his theory. Bohr was an applied magnetic field. The value of the spin angular mo-
able to derive an equation which correctly reproduced the mentum was later revised to (&/2)h and it could have com-
spectral frequencies observed in the hydrogen spectrum.
Bohr's treatment represented quite a triumph at the time even
though it was unable to explain the spectra for elements with a fourth quantum number, the spin quantum number (m, =
Z > 1and did not account for the so-called "fine structure" was added to the three already ohtained from the
of the hydrogen spectrum. Schriidinger equation.
The Bohr-Sommerfeld Model The Dirac Equation
In the Bohr-Sommerfeld model (1916) it was assumed that According to the postulates of quantum mechanics, the
the electron traveled in an elliptical path with the nucleus wave equation for ij/ is obtained from the classical expression
located at one focus. This resulted in the introduction of a for the total energy of the system by replacing the dynamical
second quantum number since two polar coordinates, r a n d variables with operators and by the insertion of the wave
0, were now needed to locate the position of the electron.
Sommerfeld also took relativistic effects into consideration.
+
function as the operand.
Dynarnicnl variable Operator
An electron in a circular orbit has constant velocity, but an Position: X, y,z r,y,z
electron in an elliptical orbit has velocity that is different a t
different positions, speeding up when it is near the nucleus
and slowing down when it is far away. The relativistic mass
of the electron changes with the changing velocity of the
electron. By taking into account these relativistic effects,
Sommerfeld was able to account for the fine structure in the
hydrogen spectrum. However, there were still many aspects a
Total energy: E ih-
of atomic spectra which remained unexplained, most at
notably: According to Einstein's special theory of relativity, the energy of
a part,iclr is given by
1) The relative intensities of the transitions: and
2) The spectra of elements with Z > 1. E" cC2( p r Z + p Y+Pp z 2 + mO2c2). (1)
Taking
The Schrodinger Equation
In 1926 the laws or postulates of quantum mechanics were E = i c (p,2 + p Y 2+ p Z 2t mo2c2)112
developed by Erwin Schriidinger resulting in his famous and applying the above postulate of quantum mechanics, one
equation. At about the same time, Werner Heisenherg, Max obtains:
Born, and Pascual Jordan developed a treatment called matrix
mechanics, which gave results which were later shown to be
equivalent to those ohtained by Schriidinger. Solutions to the

112 Journal of Chemical Education

Unfortunately, the group of mathematical symbols inside the
radical has no meanine. Dirac solvedthe ~roblemhv assuminn
the relationship
p , 2 + ~ y+ap i 2 + moacZ=(a,p, + asp, + aipi + i3mo~)2.(3)
The a's and P a r e terms which will be evaluated later. This
then gives as the total energy,
Dirac chose to use the negative root. He then applied the
ahovementioned postulate of quantum mechanics to obtain
This is the time dependent form of the Dirac equation. The
a's are cclled the Dirac velocity operators and /3 is the Dirac
aspect operator. The problem of evaluating these terms re-
mains. In order to do this we return to eqn. (3) and multiply
out the expression on the right side of the equation, ob-
taining
+ ~ Z C ( ~ P Z P ,+ U.Z~ZPZPI + arPplmo~
+ Uyazp,pz + a y Z ~ , 2+ %CZIP>P~+ ~ ~ ~ , 3 p , m ~ c
+ ~ , ~ Z P , P+Za,n,p,p, + a z Z ~ , Z+ a,O~,m,,c
+ Bazm,cpz + Oaymoe~,+ P a , r n , , ~+~p2mOZc2 ~ (6)
Inspection of the right side of eqn. (6) reveals that if the
eaualitv is to hold. then all of the cross uroduct terms. that is
s ,
all the terms located off the diagonal, must add out. This may
be accomnlished if each uair of terms svmmetricallv located
about the diagonal adds u p to zero. For example, a,a,p,p,
+ a,a,p,p, = 0. Now p,p, = p,p, since the momentum op-
erators are commuting operators. That is to say, it makes no
difference whether $ is differentiated first with respect to x
and then 2 or with respect to z first and then x . This requires
that the a's and fl anticommute, that is
. .
a,a, = -a,%, L # 1
uip = -0%
Furthermore, inspection of the diagonal reveals that in order
for the equality to hold, the following must he true: cua2 = P2
= 1.
Dirac was ahle to show that these restrictions could not be
satisfied if the a's and @ were scalar functions. He went on to
show that they had to he at least 4 X 4 matrices and $ a 4-
component vector.
It is usually written
Table 1.
Symbol Name Allowed Values
n Principal I , 2 . 3 . 4 . ..
! Azimuthal 0.1.2 . . . ("-1)
i Angular momentum +I!* %I
rn Magnetic -j.-it1.j-1,)
The probability density is given by
r $11
Multiplying out the matrices gives
The Dirac velocity operators and aspect operator are usually
given as follows:
Introducing the 4 X 4 matrices into the Dirac equation leads
to four differential equations. Solutions to the equations give
$1, $2, $3 and $a as functions of the polar coordinates, r, 4, and
0 and, unlike the Schrodinger equation, introduce all four
quantum numbers. There is not, however, a one to one cor-
later.
The Dirac equation was solved for a hydrogen-like atom by
C. G. Darwin in 1928, the same year that Dirac published his
work. The equation is not solved here, and the reader is asked
to refer to Bethe and Salpeter (1j for the solution to aparticle
in a one-dimensional box.
Consequences of the Dirac Treatment
The hydrogen spectrum When the Dirac theory is applied
to the hydrogen atom, it correctly predicts the entire spec-
trum, including all fine structure. Well, almost. In 1947 Willis
E. Lamb, Jr. and Robert C. Retherford were ahle to show that
the 2s1/2 level was higher in energy than the 2p1/2 level by
1,060MHz. This amounts to about two parts per million when
compared with the frequency of the Balmer-alpha line, which
represents the energy difference hetween t h e n = 2 and n =
3 levels. The Dirar theory predicts that these states should
have the same energy. This very small shift, called the Lamb
shift, is explained in a theory called quantum electrodynamics.
According to this theory there exist electromagnetic field
fluctuations which are auantum mechanical in nature and
the nucleus when they are close together. The shapes of the
2s1/2 and 2~112orbitals are such that the electron spends more
The Dirac Quantum Numbers
Property Principally Determined
Size and energy of orbital. analogous
to Schrodinger atom.
Designated by the letters s. p. d. f etc.
It no longer represents the orbital
anguiar momentum and no longer determines
the shape of the orbitals.
Contributesto the orbital energy and
shape. Uiually written as a subscript
following the designation for .! Sometimes
called the inner quantum number.
The magnetic quantum number together with
the angular momentum quantum number
determines the orbital shapes.
Volume 60 Number 2 February 1983 113
time close to the nucleus when in the 2 s l orbital ~ thus re- of negative energy could not be observed because there was
sulting in its having a slightly higher energy. The Dirac no way for them to interact with energy since all the negative
treatment nealects these field fluctuations and assumes the energy states were already filled. However, Dirac went on to
electromagne&c fields to behave classically. postulate that if energy in excess of 2mc2could be applied to
Dirac quantum numbers: The Dirac quantum numbers are an electron in a negative energy state then that electron could
given in Table 1. be promoted into a positive energy state where i t could be
The electron spin. An inspection of Table 1reveals that observed as an ordinary electron. Furthermore, the "hole" left
although" there are four Dirac auantum numbers. there is no
spin quantum number. The concept of the electron spinning
about an axis through its center is foreign to the Dirac treat-
ment. All of the magnetic properties of the electron may he
accounted for hv its circulational motion. Powell (3) ex-
plains
"If a physical visualization of 'spin' be needed, it is perhaps better to
think of it as the lower limit of circulational motion below which the
electron will not drop. The electron appears to be a particle which
doesn't like to move in straight lines-it insists on moving in helical
spirals wherever it goes."
The Pauli ~rincivle.The Pauli ~rincivleand the ensuing-
exclusion principle must be tacked onto the nonrelativistic
version of auantum mechanics as additional postulates but
are naturai consequences of a more gene& relativistic
quantum mechanics (reference (21, page 308).
Orbital shapes. The shapes of the orhitals are determined
by j and m. Orbitals with the same values for j and m have the
same shape. Thus, the sl/z andpyz orhitals hy necessity have
m = fl/z and all have the same shape, namely they are all
spherically symmetrical. The term "shape" is being used
somewhat incorrectly here; "angular distribution" would be
more accurate. Some organic chemists may he upset to learn
that the three 2p orbitals are shaped like a sphere (2 p1/2). a
-
douehnut 12 ", -.m = 31") and a ball that has been saueezed
. '02i?.
in around its equator (2 ~312,m = However, a set of mu-
. .
tuallv-~ernendicular D orhitals havine " the shaoe of the 2 .
m = 112 orbital can be constructed from a linear combination
van.
-, -.

of the Diracp orbitals.

All of the Dirac orhitals have electron densities which are
symmetrical about the Z axis and all have a plane of symmetry
perpendicular to the Z axis. None of the Dirac orbitals have
nodal planes ( 3 , 4) and thus the question, "How does a p
electron get from one lobe t,o the other if it cannot pass Figwe 1. Schematic diagram of the energy levels of hydrogen according to the
through the nodal plane?" can be answered by noting that Dirac theory. The Lamb shin is shown lor the n = 2 levels. The value of the
according to the Dirac treatment there are no nodes. The quantum number m is bracketed.
reas<.:isfor the absence of nodes is explained very nicely by
Poweil(3) in his excellent paper. The reader is strongly urged
to read this paper for a more complete discussion of some
other aspects of relativistic atomic orbitals. Very briefly, the
absence of nodes is due to the fact that all four components
of IL never have nodes all in the same dace. Powell also noints
out that the correct results could also he obtained by anon-
relativistic treatment if the calculations were carried out with
the correct handling of the angular dependence for an electron
with spin. The angular distribution plots commonly shown
in textbooks are for the nonexistent spinless electron. Figures
1,2, and 3 show some Dirac orhitals. These figures have been
reproduced from Szabo's paper (5).
The positron. WhenDirac applied his method to the motion
of a fr& electron, i.e., an elect& on which no outside forces
are acting, he obtained as its energy

According to this equation, there exist for the electron two sets
of energy states, one of positive energy and one of negative
energy. These two sets of energy states would range in energy
from +me2 to plus infinity and from -mc"o minus infinity.
Dirac recognized that all observed electrons occupied the
positive energy states. This then created the question, "Why
don't the electrons of positive energy spontaneously fall into
the neeative enerw states with the release of enerev?". Dirac

114 Journal of ~ h e m i c s Education

l
in the negative energy states could he observed and would
have all of the properties of a positively charged electron.
When an electron of positive energy eventually falls into this
"hole" the electron and the "hole" would hoth disappear and
an amount of enerev in excess of 2mc2 would he released.
Thus, in 1930 ~ i r a c k e d i c t e dthe existeace of the positron and
the uhenomena of uair uroduction and uair annihilation. The
poskron was disco~eredexperimentallytwo years later by Carl
D. Anderson.
Relativistic Effects on Chemical Properties
The Schrodinger treatment with the added postulates of
spm and the Pauli principle is sufficient for dealing with the
lighter elements. A perturbation method may be added for
dealing with the relativistic effects encountered in the ele-
ments of intermediate atomic number. But the heavy elements
require a fully relativistic treatment based upon the Dirac
eauation.
When the Bohr treatment is extended to hydrogen-like ions,
the equation for the Bohr radius becomes

This should apply equally well to atoms with n equal to 1or

2 since shielding would be unimportant. Solving Bohr's mur
= nh for u , substituting eqn. (7) for r and letting n equal 1
gives
e2Z
"=-
(47%)R
In atomic units, the system of units where me = h = e = a, =
1,this equation becomes
In atomic units the speed of light, c, is -137 a,". Thus, for the
heavy elements, the s electrons are approaching the speed of
light and relativistic effects are important. Let us take mer-
cury with Z = 80 for an example. The relativistic mass is given
by
Figure 3. A 3dorbital: j = 512: m = +312
(8)
pansion and destabilization of the d and f orbitals. These two
effects, the relativistic contraction of the s orbitals and the
expansion of the d and f orhitals, may he illustrated by the
ionization potentials of Zn, Cd, and Hg, as shown in Table
2.
-.
Notice that hoth the 1st and 2nd ionization potentials which
involves electrons, drop from Zn to Cd hut jump back up
again in Hg. The 3rd ionization potential, which involves the
. from Zn to Cd and drous even more sharulv
d electrons.. droos . <

With u = Z = 80 and c = 137, we obtain m = 1.2 m,. So the
masses of the 1s electrons in mercurv are increased bv ao-
appears in the denominator. PyYkk6 and ~ e s c l a u x(6) state
that "all the others shells. UD to the valence shell, contract
roughly as much because their electron speeds near the nu-
cleus are cornoarable and the contraction of the inner part of
the wave fmlction pulls in the outer tail?." They also point out
that the I, orbitals also contract: "The magnitude of the con-
traction of thep,,, subshell is comparablito that of thesln.
The p:j,, subshell contracts much less." This contraction re-
sults in a corresponding increase in stability. The relativistic
contraction of the s orhitals of the heavy elements and the
corresuondinr increase in stahilitv accounts for the inert oair
6p2) favors the +2 oxidation state.
A second consequence of the relativistic contraction of the
a and p ~ , , orbitals is that now they are more effective a t
screening the d and f orbitals from the nuclear attraction. The
d and f orbitals do not "penetrate" the way the s a n d p orbitals
do hecause of their high angular momenta and consequently,
the d and f electrons spend much less time near the nucleus
and do not experience the high velocities necessary for the
relativistic contraction. The increased shielding due to the
contraction of t h e and p orhitals thus results in a radial ex-
'It should be noted that since this derivation is based upon the Bohr
model it is, at best. a rough approximation.
from Cd to Hg.
In eoine down Grouu IA and Grouo IIA. the atomic radii
reach; maximum w i t h ~ (26.2
s nm) &d ~ a ' ( 2 l .nm).
l Fricke
and Waber (7) have calculated the atomic radii of eka-fran-
cium and eka-radium to be 25.5 nm and 21.6 nm, respectively.
Thus, accurding to these authors, the relativistic contraction
of the valence s shell overtakes the shell-structure expansion
after Cs and Ba, making Cs the largest atom in nature.
Pitzer (8)has calculated the energies of the s and p valence
orbitals for Ge, Sn, and Pb. In one set of calculations, he took
into account relativistic effects and in the other set he did not.
T h e energy differences between the s and p orbitals as ob-
tained hy the two methods are shown in Table 3. Since in the
relativistic method the and py2 orbitals have different
wei&ted averages were ;sgd for the p orbitals when 4 ~(rel:
..
enerpies and since the 0 2 1 7 orbital is doublv" degenerate.
ativistic) was calculated. Notice that 46 (non relativistic)
decreases from Ge to Sn to Ph while AE (relativistic) decreases
from Ge to Sn and then i u m ~ back
s UD for Pb. This is caused
by a decrease in the energy o? the rela$vistic s orbitals relative
to the nonrelativistic ones in going down the column.
A particularly interesting manifestation of relativistic ef-
fects is found in the unusual chemical properties of Au when
compared with Ag or Cu. The differences hetween Au and Ag
appear to he largely relativistic. Both have the electronic
configuration (n - 1)d l 0 ns'. Relativistic effects result in the
s electrons being more tightly hound and the d electrons being
more loosely bound in Au than in Ag. This results in the first
ionization potential being greater for Au (9.22 eV versus 7.57
eV) and the second ionization potential heing greater lor Ag
(21.5 eV versus 20.5 eV). The energy difference between the
(n - 1) d and ns orbitals drops from 5.2 eV for Ag to 2.6 eV for

Volume 60 Number 2 February 1983 115

 Table 2. Ionization Potentials for Group II B

Electronic Ionization Potential (eV)

Element Configuration I I1 111

Zn (Ar) 3d'04s2 9.4 18.0 39.7

Cd (Kr) 4s'%s2 9.0 16.9 38.2
Ha iXei 4f%d'06s2 10.4 18.7 34.5

Table 3. Energy Difference Between the s and p Orbitals ol the
Valence Shell
Element A 1rel.r Ar Inonre1 I
Au (8). The more tightly hound ns orbital of Au results in Au
having a much higher electron affinity (2.308 eV) than either
Ag (1.202 eV) or Cu (1.226 eV). This in turn accounts for the
formation of CsAu and RhAu which are nonmetallic semi-
conductors with the CsClstructure. Ag doesnot form any such
compounds. The relativistic contraction and tighter binding
of the 6s orbital of Au also accounts for the unusually high
dissociation enerev of Au? 12.34 eV) com~aredwith Ae? 11.65
eV) or Cue (1.95 e?). Lee et. al. (9) have attributed abo;t 1eV
of the 2.34 eV to relativistic effects. The remarkahle stabilitv
of Hg22+ must also he due to relativistic effects inasmuch as
is that binds formed hetween p112 orbitals are not strong.
Thallium (Pt 6s2 6p1) for example is extremely weakly bound
in T12 (10).I t has already been noted that new orbitals could
in the size of the atoms and ions from La to Lu. The most
i m ~ o r t a ncause
t of this contraction is the ineffective shielding
of bne 4f electron by another which in turn is caused by the
"nonpenetrating" nature of the {orbitals. Thus, the steady
buildup of nuclear charge which accompanies the filling of the
41 orbital coupled with the ineffective shield in^ results in a
steady decrease in size. Pitzer ( 8 ) has shown that these con-
siderations alone would make Lu3+ the same size as Y3+ hut
that relativistic considerations are needed to account for the
0.03 A by which Ln3+ is smaller than Y+3. Pitzer estimates
that about 10% of the lanthanide contraction is due to rela-
tivistic effects.
Conclusion
Relativistic effects have been shown to be lareelv respon-
effect, contribute to the lanthanide contraction (6,8) a& are
probably responsihle for the unusual stability of Hgz2+.These
and many other examples are discussed in the extensive review
by Pyykko (11).
I believe that the Dirac treatment and its consequences have
a definite place in the undergraduate curriculum and should
he receiving considerably mire emphasis than they are given
at present.
Literature Cited
(11 Bethe,H. A , m d Salpeter. E. E., "Quantum Meehsnica of O n e and Two-Electron
Afomr,"A~ademicPress. New Ynrk, 1957.
(2) Sherwin, C. W., "Quantum Mechanics," Halt, Rinehart and Winston, New York,
19CP

be constructed from the pl,, and p312 orbitals which would
have similar angular properties and bonding characteristics
as the Schrodinger p orbitals, but this is not favored by the
heaw elements where relativistic effects result in lame enerrv
diffeiences between thepl12 andp,?,~ states. In TI t i e energ;
difference hetween the 6 ~ l i i a n d6D:w states is nearlv 1eV.
13) Powe1l.R. E., J.CHEM.EDUC., 15, 668 11968).
(4) Whits,H. E., F'hys. Reu.,38,613 (19511.
(5) Szaba, A , J. CHeM EDuc.. 66,678 (1969).
ifilI'yykkil,P., and Desclaux, ,I. P., Acc C h e m Res, 12,276 (1979).
(71 Fricke,B.,nnd Waber. J. T.,J Chrm. Phys.. 56,3246 (1972).
(8) Pit9.er.K. S..Ari Chem K e r . 12. 271 (1979).
(9) Lee. Y. S., Ermler, W. C., Pitrei. K. S., and McLean, A. D.. J. Chem. I'hir., 70, 288
,..,,",.
,,,3,0,

110) Chrirtlunsen, P. A,. and1'itzer.K. S , J Chc,m ?hyr..74,1162 118811

The "lanthanide ~ o n t r i d i o nc' ~o & & of a steady dkcrease ( i l l Pyykk",P.. Ada. Q u u l u m Chrm., 11,353 11978).

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The Royal Society of Chemistry has organized a series of residential courses for practicing chemists who have some
knodedge of a field and are seeking a deeper understanding of the subject. The courses for 1983 are:
"Mass Spectrometry," 18-22 April 1983, U.M.I.S.T.
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"Heterogeneous CaLalysis," 25-28 July 198% King's College, Cambridge
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116 Journal of Chemical Education