Research: Science and Education
The Particle inside a Ring: A Two-Dimensional Quantum
Problem Visualized by Scanning Tunneling Microscopy
Mark D. Ellison
Department of Chemistry, Ursinus College, Collegeville, PA 19426; mellison@ursinus.edu
Quantum mechanics is central to an understanding of
modern chemistry. However, it is a difficult subject to teach and
one that students have great difficulty grasping (1). It has long
been recognized that incorporating aspects of modern research
is one way to increase student interest in a subject (2), yet such
examples can be difficult to find in quantum chemistry. A bal-
ance must be struck between mathematical straightforwardness
and physical relevance. Often, examples lean toward mathemati-
cal tractability so as not to overwhelm undergraduate students.
This approach has the advantage of allowing students to become
familiar with solutions to the Schrdinger equation but often
leaves students grasping for links to physical systems with which
they are familiar.
B details might be beyond the level of an undergraduate physical
Figure 1. (A) STM image of electron density in a ring of Fe atoms
on a Cu(111) surface and (B) cross section of the image. From
Crommie, M. F.; Lutz, C. P.; Eigler, D. M. Science 1993, 262,
218220. Reprinted with permission from AAAS. Reprint Courtesy
of International Business Machines Corporation, copyright
International Business Machines Corporation.
1282 Journal of Chemical Education Vol. 85 No. 9 September 2008 www.JCE.DivCHED.org Division of Chemical Education
One such physical system that is presented in nearly every
undergraduate physical chemistry textbook is the one-dimen-
sional particle-in-a-box model (320). This model is well-suited
for the students first exposure to the Schrdinger equation. The
fact that the potential inside the box is zero makes the solution
of the resulting ordinary differential equation rather clear-cut.
Additionally, the imposition of boundary conditions clearly
leads to quantized energy levels in the system. Thus, the particle-
in-a-box model does indeed serve as a valuable introduction to
the Schrdinger equation and its important implications for
bound systems. However, the particle-in-a-box model has, at
best, a somewhat tenuous connection to real physical systems.
There are, of course, the well-known laboratory experiments
using cyanine dye molecules (2123). A slight modification to
a particle-on-a-ring system allows for a crude model of the elec-
tronic structure of benzene (4, 7, 13, 14, 16). However, the fact
that these models make only qualitative connections to actual
physical systems is a serious drawback.
This need not be the case, for there are a number of
examples from modern science that can be used to illustrate
quantum mechanics. One such area of active research that
should be known to physical chemistry students is scanning
probe microscopy (SPM), which generally encompasses two
complementary techniques, atomic force microscopy (AFM)
and scanning tunneling microscopy (STM). These experimen-
tal techniques have, for example, enabled scientists to measure
forces involved in stretching DNA molecules (24), to visualize
elementary steps of chemical reactions (25), to probe the elec-
tronic structure of surfaces (26), and even to manipulate single
atoms (27). The high-resolution imaging made possible by AFM
and STM can stir students imaginations and motivate them to
learn more about the underlying science.
STM in particular can be used to illustrate several topics in
quantum mechanics. Many physical chemistry textbooks discuss
tunneling in some detail (35, 713, 15, 18, 19). Although the
chemistry course, students can grasp the qualitative features of
tunneling, such as the exponential dependence on tipsample
distance (28). Recently there has been some debate in this
Journal about the exact nature of the image (2932), but it is
generally recognized that an STM image reflects the overlap of
orbitals in the tip and sample (33). This allows STM to observe
the wavelike nature of matter directly.
In 1990, researchers at IBM published their work on us-
ing STM to manipulate Xe atoms on a Ni surface in ultrahigh
vacuum and at very low temperatures (27). By adjusting the
tipsample voltage, they were able to pick up individual atoms
and deposit them at specified locations on the surface. Shortly
thereafter, the researchers arranged Fe atoms in a circular pat-
tern of average diameter of 142.6 on a Cu(111) surface and
observed standing electron waves within this quantum corral,
as shown in Figure 1A (34). Another study imaged the stand-
ing waves at steps on a Cu(111) surface (35). The visual images
 Research: Science and Education

of the electron waves are striking and directly demonstrate the z

wavelike nature of matter (36). Additionally, they can be quan-
titatively understood using the two-dimensional Schrdinger
equation. Therefore, a particle confined to a circular well, or a r0 R = 90p
particle in a quantum corral, is a suitable example for students
y
that shows an application of the quantum mechanics to a physi- r
G
cally real and interesting system. N
Introducing the particle-in-a-quantum-corral model
x
to students after the particle-in-a-box model has additional
advantages. First, it extends the solution of the Schrdinger Figure 2. Coordinate system and variables for a particle in a quantum
equation to a system in two dimensions. This is a more natural corral. The corral is a circle of radius r0 in the xy plane.
progression than the typical jump from a particle in a one-
dimensional box to a particle in a three-dimensional box. Sec-
ond, the solution involves separation of variables, preparing the
students for use of this technique to find the solutions to the
Schrdinger equation for the hydrogen atom. Third, the solu-
tion to the Schrdinger equation for the particle in a quantum with respect to derivatives of r and R is a constant with respect
corral involves an established differential equation with known to derivatives of :
solutions, the Bessel equation and Bessel functions, respectively.
2
When presented with the solution to the Schrdinger equation h 1 v 2 vR 1 v2 '
for the hydrogen atom, students are, in short order, introduced  ' 2 r  R 2  ER ' (2)
to two known differential equations with known solutions (the
2N r vr vr r vG 2
Laguerre and Legendre polynomials). The fact that known dif-
Next, divide both sides by R, , and the constants outside the
ferential equations with known solutions result from solving the
brackets:
Schrdinger equation is obvious to teachers but not necessarily
to students. Solving the Schrdinger equation for the particle in 1 1 v 2 vR 1 1 v 2 ' 2 NE
r    2
a quantum corral introduces this idea simply, making students (3)
familiar with it once the Schrdinger equation for the hydrogen R r 2 vr vr ' r 2 v G2 h
atom is solved. These advantages plus the connection to a real-
Now multiply both sides by r 2 and collect terms dependent on r
world example that is visually captivating make the particle in a
on the left side and terms dependent on on the right side:
quantum corral a useful system to present in an undergraduate
quantum chemistry course. Of the many physical chemistry 1 v 2 vR 1 v2'
2 N E 2
and quantum chemistry textbooks that I inspected (320),  r  2
r  (4)
only the one by Berry, Rice, and Ross (7) presents and solves R vr vr h ' v G2
this system.
The left side of eq 4 has terms that depend only on r, and the
right side has terms that depend only on . Because r and are
Introduction to the Model independent variables, the only way the two sides of eq 4 can
be equal is if they are equal to the same constant. Following
A schematic of the system is shown in Figure 2. A particle
the convention of the solution of the Schrdinger equation for
of mass is confined within a circular region of radius r0. The
the hydrogen atom, we let each side of the equation equal the
spherical coordinate system is used, with r being the distance
constant m 2:
between the particle and the origin, being the angle between
r and the x axis, and having a constant value of 90 or /2. We
1 v2' (5)
assume that the potential inside the corral is zero and that the  m 2
particle cannot escape the corral. That is, V = 0 for 0 r < r0 and ' v G2
V = for r r0. With constant, the Schrdinger equation for
1 v 2 vR 2 NE 2
this system simplifies to  r  2
r  m 2 (6)
R vr vr h
2 2
h 1 v 2 v  1 v :  E : Equation 5 is exactly the same as what will be obtained for the
 r (1)
2 N r 2 vr vr r 2 vG 2 part of the hydrogen-atom solution. It rearranges to

v2'
 m2 '  0 (7)
Solution of the Model vG 2
Because r and are independent variables, a natural ap- which has the solutions
proach is to posit that the solution will be a product of functions '  A e q i mG (8)
of the individual variables: (r,) = R(r)(). That is, separate
the solution into the product of a radial part and an angular 1/2
where i = (1) and A is a normalization constant. Because the
part, the same approach that is used for the hydrogen atom. wavefunction must be single-valued, the circular symmetry of
Substitute this expression into eq 1, noting that is a constant the system means that () = ( + 2). This condition restricts

Division of Chemical Education www.JCE.DivCHED.org Vol. 85 No. 9 September 2008 Journal of Chemical Education 1283
 Research: Science and Education

v= 0 Table 1. Values of x for Which the Bessel Functions

1.0 v= 1 J0, J1, and J2 Are Equal to Zero
0.8
v = 1
0.6 J0 J1 J2
0.4
2.405 3.832 5.136
Jv(x)

0.2
0.0 5.520 7.016 8.417
0.2
0.4 8.654 10.173 11.620
0.6
0 5 10 15 20 25 11.792 13.324 14.796
x
14.931 16.471 17.960
Figure 3. Bessel functions J0, J1, and J1.

the values of the quantum number m in eq 8 to 0, 1, 2, 3,
and so forth. This is the solution to the angular part of the prob-
lem, and we now turn to the solution to the radial part.
Starting with eq 6, bring m2 to the left side and multiply
both sides by R to obtain
v 2 vR 2 N E
These functions oscillate sinusoidally, and the amplitude steadily
decreases as x increases. Unlike the sine and cosine functions,
however, the Bessel functions do not equal zero at regularly
periodic intervals.
Energy Levels of the System
r  R r 2  m2R  0 (9)
vr vr h
2 The total wavefunction, then, is

Taking the derivative of the first term and factoring R from 1

2 NE 2 (15)
the second and third terms yields :  N Jm 2
r ei m G
h
vR v2R 2 N E 2
2r  r2  2
r  m2 R  0 (10) where N is a normalization constant. To satisfy the boundary
vr vr 2 h
condition = 0 for r r0, the Bessel function must equal zero
Then rearranging, we finally have at r = r0. As in the particle in a 1-D box, the application of the
boundary condition results in quantization of the allowed ener-
v2 R vR E 2
2N gy levels. However, unlike the particle in a 1-D box, there are no
r2  2r  2
r  m2 R  0 (11) analytical expressions for the x values at which the wavefunction
vr 2 vr h for the particle in a quantum corral is zero. However, applied
mathematics textbooks have tables of Bessel function values that
This is a form of Bessels equation that appears frequently in sci-
allow the determination of x values at which the Bessel function
ence and engineering, particularly in situations with cylindrical
is zero (38). Alternatively, these x values can be determined
symmetry (3739), such as the particle in a quantum corral.
graphically or by using a symbolic mathematics engine such as
Specifically, eq 11 is analogous to
Mathcad (40), Maple (41), or Mathematica (42). Because J1 =
d 2y J1, these Bessel functions both equal zero at the same x values.

x2
dx 2
 x
dy
dx


 B2x2  v 2 y  0
(12) Table 1 lists x values at which the first few Bessel functions equal
zero. Also, for |m| > 0, Jm = 0 at x = 0, but this is a trivial solu-
tion, because it would imply a corral of zero radius.
Comparing eqs 11 and 12 shows that = (2E/h2)1/2. Be-
Consequently, for m = 0, the allowed energy values are
cause m is an integer, the solutions to eq 11 are Bessel functions
of the first kind, Jv(r) and Jv(r) (38, 39). Bessel functions are 2 2 2 2 2 2
a convergent infinite polynomial series, and Bessel functions of h 2. 405 h 5.5520
h 8. 654
E  , , , | (16)
the first kind are given by the following formulas (38, 39) 2N r0 2N r0 2N r0

e
1
p x 2 p This result can be extended to a more general formula for any
Jv x
 x v 2 2 p  v p ! v  p
!
(13)
value of m
p 0
2
For integer v, the following condition holds h
E  z n,m2 (17)
2 N r02
J v x
  1
Jv x

v
(14)
where zn,m is the nth zero of the Bessel function Jm (Table 2) and
Because the Bessel functions are series functions, their graphi- n and m can be thought of as analogous to quantum numbers for
cal form is not readily apparent. Figure 3 shows J0, J1, and J1. this system. In particular, n is analogous to the quantum number

1284 Journal of Chemical Education Vol. 85 No. 9 September 2008 www.JCE.DivCHED.org Division of Chemical Education
 Research: Science and Education

Table 2. Energy Values for Low-Lying 71.3 Radius

Quantum Corral Energy Levels

Energy/J

Relative Energy
n |m| = 0 |m| = 1 |m| = 2

1 6.945 1022 1.763 1021 3.167 1021

2 3.659 1021 5.911 1021 8.507 1021

3 8.993 1021 1.243 1020 1.621 1020

4 1.670 1020 2.132 1020 2.629 1020 |m| = 0 |m| = 1 |m| = 2

5 2.677 1020 3.258 1020 3.873 1020
Figure 4. Energy Levels of the quantum corral system.

for a particle in a 1-D box, whereas m is an angular momentum
quantum number. As an illustration, for an electron in a cor-
ral of radius 71.3 , corresponding to the STM-constructed
quantum corral (34), the energies of the first five levels are given
in Table 2.
The relative energies for the energy levels in Table 2 are
shown in Figure 4. Note that, for |m| > 0, the levels are doubly
degenerate because the energy depends on |m|. The energy levels
for a particle in a quantum corral are qualitatively similar to
those of a particle in a 1-D box in several ways. First, the spac-
ing increases as energy increases. Second, the energy is inversely
proportional to the square of the radius of the corral, so a small
corral will have large energy spacings whereas a large corral will
have small energy spacings. Finally, the energy is inversely pro-
portional to the mass of the particle, so the lighter the particle,
the more pronounced the wave nature of the system.
Wavefunctions and Probability Distributions
The form of the wavefunctions for the particle in a quantum
corral is given in eq 15. Because the Bessel functions are an infi-
nite series, it is not possible to write the complete wavefunction
explicitly without truncating some of the terms. The wavefunc-
tions are of particular interest in terms of the probability of
finding the particle, which is proportional to *. Because the
Bessel functions are real, the probability can be expressed as
2
1
2NE 2
:* : u Jm 2
r e i m G e i m G
h
1 perimental data, the prediction of the probability of finding the
2 NE
 Jm
2
h be compared to the STM data. The STM researchers used scan-
The integral of the square of a Bessel function does not have a
closed analytical form, so finding the normalization constant
in eq 15 is not straightforward. It is possible, however, to work
with non-normalized wavefunctions and make comparisons of
relative probabilities.
STM measures electron density (33), which is related to
*. Therefore, graphs of the square of the Bessel function can
be used to make comparisons to the STM images. Figure 5AC
shows the top and perspective views of J02, for n = 1, 3, and 5,
respectively, of a 71.3 radius quantum corral. Figures 58 were
generated by plotting eq 18 in MathCad (40). White and light
gray represent a high probability of finding the particle, and dark
gray and black represent a low probability. It is apparent that as
n increases, so does the number of nodes. For lower n, there is a
larger probability of finding the particle near the center of the
ring, whereas as n increases, so does the probability of finding
the particle farther away from the center of the ring.
Figures 6 and 7 display the relative probability distribution
for |m| = 1 and |m| = 2, respectively. Similarly to Figure 5AC,
these figures display the probability distributions for n = 1, 3,
and 5, respectively. The probability distributions for |m| > 0 are
distinctly different for those for m = 0. First, for |m| > 0, the
probability of finding the particle near the center of the ring is
low, whereas it is high for m=0. Second, although it is difficult
to see, these distributions are broader than those for m = 0.
The main feature, however, of these probability distributions
is the low probability of finding the particle near the center of
the ring.
The probability distributions for |m| = 1 and |m| = 2 have
the same number of radial nodes and are similar in appearance.
Indeed, the differences between them are subtle. For |m|=1,
the central ring is taller, but the successively outward rings
are shorter than those for |m|=2. Also, the rings for |m|=2
are broader than those for |m|=1. This pattern continues for
increasing m.
Modeling Electron Waves
(18) Because the ultimate test of a model is comparison to ex-
2
2
r electron made by the particle-in-a-quantum-corral model should
ning tunneling spectroscopy to determine which energy levels
were populated during the experiment. Their results indicated
that the electrons were predominantly in the states (n,m) = (5,0),
(4,2), and (2,7) (34). The authors fit their STM data to a linear
combination of the probability distributions of these states and
found good agreement between their data and the fit, as shown
in Figure 1B. This experimental validation indicates that the
particle-in-a-quantum-corral model works well to describe
the electron waves observed when electrons are confined to a
circular region of the surface of a metal. Figure 8 shows a linear

Division of Chemical Education www.JCE.DivCHED.org Vol. 85 No. 9 September 2008 Journal of Chemical Education 1285
Research: Science and Education

A B C

Figure 5. (top) Top view, (bottom) perspective views of the relative

probability of finding a particle in a quantum corral for m = 0 and
(A) n = 1, (B) n = 3, and (C) n = 5.

A B C

Figure 6. (top) Top view, (bottom) perspective views of relative

probability of finding a particle in a quantum corral for |m| = 1 and
(A) n = 1, (B) n = 3, and (C) n = 5.

A B C

Figure 7. (top) Top view, (bottom) perspective views of relative

probability of finding a particle in a quantum corral for |m| = 2 and
(A) n = 1, (B) n = 3, and (C) n = 5.

Figure 8. (top) Top view, (bottom) perspective view of relative

probability of finding a particle in a quantum corral for a linear
combination of three quantum states.

1286 Journal of Chemical Education Vol. 85 No. 9 September 2008 www.JCE.DivCHED.org Division of Chemical Education

combination of the square of the Bessel functions corresponding
to the above three states. It is in good qualitative agreement with
the STM data (Figure 1), correctly showing five ripples in the
pattern, the largest peak in the center, and larger gaps between
peaks 2 and 3 and peaks 4 and 5. These results provide further
confirmation of the wave nature of matter and demonstrate the
high accuracy with which this simple model can describe an
actual physical system.
Conclusions
The particle in a quantum corral is a model of an actual
physical system that offers several pedagogical advantages. It
extends the idea of a particle in a one-dimensional box to two
dimensions, providing a bridge between one-dimensional and
three-dimensional systems. Solution of the Schrdinger equa-
tion for this system involves separation of variables and reveals
a well-known equation with established solutions. Application
of boundary conditions results in quantization of energy, and
some of the energy levels are degenerate. The wavefunctions do
not have an easily expressible normalized form, but it is possible
to make qualitative comparisons of relative probabilities. These
probabilities agree well with STM data, indicating the accuracy
of the model. By learning about this model, students can ap-
preciate the application of quantum mechanics to understand
exciting, cutting-edge science.
Acknowledgment
I acknowledge Erica Ellison for a critical proofreading of
this article.
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