In the Classroom
Introducing Relativity into Quantum Chemistry
Wai-Kee Li*
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong
*wkli@cuhk.edu.hk
S. M. Blinder*
Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055,
United States and Wolfram Research, Inc., Champaign, Illinois 61820-7237, United States
*sblinder@umich.edu;
sblinder@wolfram.com
In the short time span between 1926 and 1928, English
physicist Paul Dirac (1902-1984) played a pivotal role in two
important developments in the history of physics: transformation
theory (a unification of Heisenberg's and Schrödinger's formulations
of quantum mechanics) and incorporating relativity into quantum
mechanics. In this article, an attempt is made to introduce the
important and chemically significant results of relativistic quantum
mechanics to chemistry students and teachers. The presentation
is essentially nonmathematical. Indeed, not a single equation is
included, so this article is mainly qualitative.
Electron Spin
When chemistry students first encounter quantum mechanics
in their physical chemistry course, the first system they treat is often a
lone electron trapped in an infinitely deep potential well, the so-called
particle-in-a-box problem (1 2,). When the box is one-dimensional,
the solutions (energy levels and wavefunctions) are characterized by a
single quantum number. When the box is two-dimensional, that is,
when it is a square or a rectangle, the solutions require two quantum
numbers. When the box becomes three-dimensional, as in the case of
a cube, the solutions will have three quantum numbers. So the moral
of the story is: in quantum mechanics, the solutions of a k-dimensio-
nal Schrödinger equation will have k quantum numbers. Indeed, the
solutions of the Schrödinger equation for the hydrogen atom (with
three variables r, θ, and j) have three quantum numbers, n, l , and
ml . The electron possesses, in additional to its orbital motion, an
internal degree of freedom called the spin. Spin is somewhat analo-
gous to the daily rotation of the earth, which complements its annual
revolution around the sun. An electron is said to have “spin 1/2”,
which, according to the arcane rules of quantum mechanics, provides
a fourth quantum number ms, with the possible values þ1/2 or
-1/2. Spin was first postulated by G. E. Uhlenbeck and S. Goudsmit
in 1925 to explain some anomalies in atomic spectra. Wolfgang Pauli
exploited this additional degree of freedom, even before the advent of
quantum mechanics, to formulate his exclusion principle, which
states that no two electrons in an atom can exist with the same set of
four quantum numbers. The concepts of spin and the exclusion
principle made it possible to understand the periodic structure of the
elements. Although electron spin was already there before Dirac
extended quantum mechanics to take account of relativity, he gave
electron spin a rigorous mathematical justification.
Dirac believed that the two great advances in 20th century
physics;Einstein's theory of relativity and quantum mechanics;
should be part of a unified theory. (Today the most challenging
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10.1021/ed100523k Published on Web 10/18/2010
unsolved problem in physics involves the unification of gravity with
quantum mechanics.) Specifically, Dirac recognized the need to put
special relativity into the Schrödinger equation. The resulting
modification of the Schrödinger equation, which describes the
relativistic behavior of the electron, gave rise to the Dirac equation.
Miraculously, the existence of electron spin automatically emerged,
without the need for any additional postulate. Also accounted for
was the electron-spin magnetic moment, a byproduct of a charged
particle with angular momentum, with the correct g-factor of 2.
(By contrast, the orbital motion of an electron has g = 1.)
To be historically accurate, it should also be pointed out that
Erwin Schrödinger actually wrote down the first relativistic wave
equation (in 1925, and in his notebook!) as he looked for an
equation to describe the de Broglie waves for electrons. When he
applied this equation to the hydrogen atom, he failed to obtain
the correct fine structure of the hydrogen spectrum because he
did not take electron spin into consideration. So he abandoned
this equation and settled for the nonrelativistic equation that
now bears his name. Two years later, Oskar Klein and Walter
Gordon resurrected this equation and found that it correctly
described the behavior of spinless particles (such as pions). So
now it is known as the Klein-Gordon equation.
Even the standard procedure for quantization of a classical
equation of motion shows the pervasive influence of relativity. The
fundamental variables of a system can be formulated as a “four
vector” (x1, x2, x3, x4), with x1, x2, x3 =
√x, y, z, respectively, and x4 = ict
(where c is the speed of light and i = -1). The energy-momentum
four vector is correspondingly defined by (p1, p2, p3, p4), with p1, p2,
p3 = px, py, pz, respectively, and p4 = iE/c (where E is energy). The
fundamental quantization prescription is then given by the operator
replacement pj f -i(h/2π)∂/∂xj, j = 1-4, where h is Planck's
constant. (In modern usage, the fourth components of the four
vectors are replaced by the real variables x0 = ct and p0 = E/c.)
Nodes of an Electronic Wavefunction
In the radial probability distribution function of a (hydrogenic)
2s electron, r2|R2,0|2, there is a node at r = 2 au (1, 2). In other words,
there is zero probability of finding this electron between r and r þ dr,
with r = 2 au, although there is finite probability of finding the
electron in the regions of r < 2 au (region I) and r > 2 au (region II).
So how can the electron go from region I to region II (or the other
way around) without going through the node? Or, in an analogy
with baseball, how can the electron go from first to third without
touching second base? Many approaches to this question have been
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 In the Classroom
evoked, from those citing the uncertainty principle to arguments that
in the quantum world an electron does not move in a classical fashion.
But an attractive rationalization is suggested by the Dirac equation.
It turns out that the Dirac electronic wavefunction ψ is a four-
component spinor;there is a twofold contribution representing the
two spin states and another duality determining whether the particle
is an electron or a positron. (The four-component wave function is
sometimes erroneously attributed to the four-dimensional structure
of spacetime in relativity, but the relativistic Klein-Gordon equation
also describes a spinless particle.) The four components of ψ, design-
ated, ψ1, ψ2, ψ3, and ψ4, give a probability density function ψ†ψ of
the form |ψ1|2 þ |ψ2|2 þ |ψ3|2 þ |ψ4|2. For the 2s wavefunction, at
r = 2 au, among these four terms, the first two are zero, whereas the
sum of the last two are minutely positive. In other words, the “node”
of the 2s wavefunction actually has a very small finite value at r = 2 au
when relativity is taken into account. So now the 2s electron can go
through the “node” at r = 2 au without any conceptual difficulty.
The Prediction of the Positron
In addition to accounting for electron spin, the Dirac equation
also unexpectedly implied that an electron can have either positive or
negative energy. To avoid this apparent dilemma, Dirac assumed
that, in a given atom, all of the infinite number of negative energy
levels are filled--this being the inherent nature of what we perceive
as the “vacuum”, whereas the positive energy levels are filled by the
electrons of that atom from the ground up. When a member of the
negative energy “sea” is excited to a positive energy state, the resulting
hole in the negative energy “sea” will appear to be a particle with a
positive charge. In 1928, only two subatomic particles were known:
electron and proton. Hence, Dirac at first thought this particle was a
proton. However, it was later shown that the hole had to have the
same mass as an electron. It cannot be a proton, so Dirac proposed
there should be a new particle with electronic mass as well as a
“positive electronic” charge, and this particle should also have a spin
of 1/2. In 1932, this prediction became a reality as Carl Anderson
observed this particle's existence in cosmic rays. He called this new
particle a “positron”.
Dirac originally got his idea about a filled “sea” of negative-
energy electrons from X-ray spectroscopy on atoms. An X-ray
photon can promote an inner-shell electron to an excited level, thus,
leaving behind a hole in the inner shell. This may be viewed as “pair
production” of a positive-energy electron plus a negative-energy
positively charged hole. When the photon falls back, an inverse
process of pair annihilation results.
From a more modern viewpoint, the heavy philosophical
baggage of an infinite Dirac “sea” can be avoided by the development
of quantum field theory. The key idea is that wavefunctions are
promoted from simple functions to particle creation and annihilation
operators. Known as second quantization, this procedure enables
electrons and positrons to be created, from a more rational vacuum.
Lastly, the positron may also be called an antielectron; it is
the antimatter counterpart of the electron. Annihilation occurs
when a positron and an electron collide, and two or more
photons (or other particles) are produced. Thus, the Dirac
equation first predicted the existence of antimatter and thereby
opened up a whole new aspect of particle physics.
Particle in a One-Dimensional Box
Now let us return to the particle-in-a-box problem, but this
time with relativity considered. The mathematical treatment (3)
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of this problem is considerably beyond the scope of this article.
Still, some interesting qualitative results can be extracted.
When the box is one-dimensional, the wavefunction ψ has just
two components, ψ1 and ψ2, and the probability density function
ψ†ψ is |ψ1|2 þ |ψ2|2. Nonrelativistically, the wavefunction (and
hence the probability density function) of the first excited state has a
node at the midpoint of the box. As we have seen, when relativity is
turned on, this node acquires a small nonzero component.
Another crucial question is: when does relativity become an
issue for this physical system? Specifically, at what box length
should we take relativity into account? As it turns out, the critical
length L0 is h/2πmc, where is m the electronic mass, and h and c
have been defined earlier. After putting in the numbers, L0 is
calculated to be about 0.004 Å. When the box length is about L0
or smaller, the electron is relativistic. So we now know we are
justified to apply the nonrelativistic free-electron model (1, 2) to
treat the π electrons of a conjugated polyene such as butadiene
because the length of this box is nearly 6 Å, or about 1,500L0.
Properties of Heavy Elements
In the special theory of relativity, when an electron is
traveling with a velocity v that is an appreciable fraction of the
speed of light, its effective mass m behaves like m0[1 - (v/c)2]-1/2,
where m0 is the rest mass of the electron. In atomic units, speed of
light c is approximately 137. Thus, the average orbital velocity Ævæ
of a 1s electron in an atom is approximately Z au, where Z is the
atomic number. Hence, for an electron in Au, with Z = 79, we
have Ævæ/c ≈ 79/137, or 0.58. So this 1s electron travels at a
significant fraction of the speed of light. Moving at this speed,
mass m of the electron increases to 1.23m0, which has a considerably
effect on the radial distribution of the electron. Recall from Bohr's
atomic theory that the radius of the nth orbit is proportional to n2/m.
Thus, the ratio between the relativistic 1s radius to its nonrela-
tivistic counterpart is approximately (1.23m0)-1/m0-1, or 0.81.
This implies that relativistic effects have contracted the 1s orbital in
Au by about 20%. Similar contractions in a heavy atom also occur for
the higher s orbitals because these become orthogonal to one
another. The result is a lowering of the energies of all s orbitals.
This can also be seen from the Bohr atomic model, where energies
are proportional to -m. When relativity is turned on, the heavier
electron makes the ground-state energy lower, or more negative. In
any event, this is known as the direct relativistic effect and accounts
for orbital contraction and stabilization of s orbitals and, to a lesser
extent, p orbitals.
In contrast, the valence d and f orbitals in Au are expanded and
destabilized by relativistic effects. This is because the contraction of
the s orbitals increases their shielding magnitude, which gives rise to a
smaller effective nuclear charge for the d and f electrons. This is
known as the indirect relativistic orbital expansion and destabiliza-
tion. In addition, if a filled d or f subshell lies just inside a valence
orbital, that orbital will experience a larger effective nuclear charge
that will lead to orbital contraction and stabilization. This is because
the d and f orbitals expand when their shielding from the nucleus is
reduced. This is also believed to make a contribution to the
lanthanide contraction.
The concomitant relativistic stabilization of the 6s orbital
and the destabilization of the 5d orbital in Au narrow the energy
gap between these two orbitals. As a result, the [...5d106s1]2S1/2 f
[...5d96s2]2D3/2 transition in Au is observed in the visible region;
this absorption of blue and violet region accounts for the yellow
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luster of gold. In contrast, the corresponding [...4d105s1]2S1/2f
[...4d95s2]2D3/2 transition in Ag (Z = 47) lies in the UV region.
In addition, the stabilization of the 6s orbital gives rise to a large
ionization energy for Au, which in turn leads to gold's greater
stability: gold does not tarnish in air, whereas silver does.
By a similar argument, the relativistic contraction of the 6s2
subshell in Hg (Z = 80) makes this element relatively unreactive:
the so-called inert pair effect described in many inorganic
chemistry texts. Indeed, the tightly bound low-energy pair of
6s electrons in Hg makes it comparable to He, nearly a noble gas.
Thus, there is reduced interatomic attraction in Hg, which is
responsible for it remaining a liquid at room temperature.
The relativistic effect on the property of heavy metals is now
a topic covered in books and journal articles (1, 2, 4, 5). This
short section gives only the highlights.
Conclusion
This article attempts to present to chemistry students and
teachers some important and chemically interesting results of
relativistic quantum mechanics. These results include a mathe-
matical justification for electron spin, a possible rationalization
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r 2010 American Chemical Society and Division of Chemical Education, Inc.
In the Classroom
of the mystery surrounding the nodes of wavefunctions, the
prediction of antimatter, the relativistic treatment of the one-
dimensional particle-in-a-box problem, and the anomalous
properties of some heavy metals. It is hoped that this nonmathe-
matical presentation will be accessible to chemists. A few
additional references (6-8) are cited for those who wish to
delve more deeply into this topic.
Literature Cited
1. See, for example , Blinder, S. M. Introduction to Quantum Mechanics;
Elsevier/Academic Press: Amsterdam, 2004.
2. See, for example , Li, W.-K.; Zhou, G.-D.; Mak, T. C. W. Advanced
Structural Inorganic Chemistry; Oxford University Press: Oxford,
U.K., 2008.
3. Alberto, P.; Fiolhais, C.; Gil, V. M. S. Eur. J. Phys. 1996, 17, 19–24.
4. Norrby, L. J. J. Chem. Educ. 1991, 68, 110–113.
5. Guerrero, A. H.; Fasoli, H. J.; Costa, J. L. J. Chem. Educ. 1999, 76,
200.
6. Pitzer, K. Acc. Chem. Res. 1979, 12, 271–276.
7. Pyykkö, P.; Desclaux, J. Acc. Chem. Res. 1979, 12, 276–281.
8. Pyykkö, P. Chem. Rev. 1988, 88, 563–594.
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