edited by
J. DUDLEY HERRON
How Does the Electron Cross the Node?
Prepared from responses written by
Russell H. Johnsen
T h e Florida State University
and
Winston D. Lloyd
T h e University of Texas a t El Paso
As introductory chemistry courses place more emphasis on
modern theories about the structure of atoms, students are
frequently confused about the meaning of concepts a t the
heart of those theories. The following question illustrates the
problem:
Atomic orbitals are frequently interpreted as the probability distri-
bution fur an electron at a given energy level. As such,all orbitals other
than the 1s show a surface representing azeroprabability separating
other regions of "on-zero probability. Far example, a 2p orbital has
two lobes of "on-zero probability separated by a planar surface of zero
probability as illustrated in Figure 1.
Figure 1. Probabilitydistribution for a 2porbitai.
Thoughtful students point out that it is illogical to assume that
there is some finite probability of finding an electron in the left lobe
and some finite prohability of finding that same electron in the right
lobe but no probability of finding it between. How does it get from one
side to the other?
Both respondents to this question indicate that the con-
fusion arises from an assumption that the electron is a particle,
when the model that produces the orbital diagram assumes
that the electron behaves as a wave. In the following com-
ments, Johnson shows how a discussion of wave behavior
might he used to clear up the confusion.
The Electron as a Wave
Brought up in a world in which particle phenomena and
their Newtonian interpretations are common place, the stu-
dent finds it difficult to make the transition required for an
understandine- of electron behavior in terms of wave me-
chanics.
In this particular instance the student is making the fun-
damental error of asking a "particle question" about a model
which views the problem in terms of the behavior of waves.
The wavefunction, or orbital, and its square (which is the
probahility distribution) arrives a t the picture of the two-
lobed 2p orbital utilizing mathematical functions which are
zero valued a t certain values of the independent variable.
A simple example of such a function is y = sin 0 for which
y is zero valued at values of 0 corresponding to integral mul-
tiples of a radians, as shown in Figure 2.
Note that the value of the function oscillates between a
Purdue University
West Lalayette, Indiana 47907
Figure 2. The graph of y = s i d , a periadic function analogous to a wavetunc-
lion.
Figure 3. The graph of the equation for the 2pz orbital.
minimum value of -1 and a maximum value of +l.In a similar
fashion the p-orbitals (one electron wavefunctions) are
zero-valued in a plane, with a positive lobe above the plane and
a negative lobe below the plane. For example, the Zp, one-
electron orbital ('P2pr)has the form
'/4(27r)-'/2 ( z / a p re-Z1/2a COSB
When r is the distance from nucleus, a is the atomic unit of
distance, and B is the angular coordinate.
Analysis of this function shows that for y = 0 (the xz plane)
the function graphs as shown in Figure 3; i.e., the xy plane is
a nodal plane in which the value of the function (and its
square, the probability distribution) is zero.
A two dimensional analog can be found by examining the
behavior of vibrating strings.
In such an analysis, it is clear that the question of the elec-
tron "crossing" the node does not arise. The picture simply
represents the value of the probability distribution function
a t a given angle and distance from the nucleus.
Lloyd takes a slightly different approach in his response
and explains why a description of the electron as a charge
cloud has certain advantages.
The Electron Cloud
The apparent paradox presented in this question is the
result of the assumption that the electron is a discrete particle
moving in such a way that the time spent a t a given position
is described by a probability function. In fact, such an inter-
pretation violates the Heisenberg Uncertainty Principle.
Uncertaintv concernine the location of the electron is about
as great as the size of thYe atom. What is shown in texts as the
s h a ~ of
e atomic orbitals is a Dart of a orobabilitv function. The
prohability function describes the probability that an exper-
iment desiened to locate the electron will eive a oarticular
result. I t is"important to note, however, thacthis Gobability
Volume 57, Number 9, September 1980 1 651
function is not time dependent; i t applies to all locations a t
the same time.
Consider what happens when we shoot electrons, one a t a
time. a t a barrier which has two closelv . spaced
. holes in it. If
we then let the electrons impinge on a phosphor screen, there
will he a tinv flash uf light each time it is hit. A time exposurr
a
of the screen will give diffraction pattern. This diffraction
pattern (probability distribution) will agree with the result
expected for two spherical waves which have their origins a t
the two holes. If you contrast this result with the result ex-
pected for discrete particles that travel in a straight line
through one or the other of the two holes, you can see that the
B ~H.A.~and ~~ ~I,.,~ " t ~~world
~h , ~of
, the tom," vol. 11,
Basic Books Inc., New York, 1966, p. 1225.
Morwick, J. J., J. CHEM. EDUC., 56,262 (1979).
652 1 Journal of Chemical Mucation
electron is behaving only as a wave, not as a particle, as it
passes the harrier.'
It is interesting to consider the probability distribution at
distances far from the nucleus. We know that the electron
cannot puss~hl)be as much as one cent:merer from the nu-
cleus, but there is a finite probability that an experiment de-
a
signed to detect electrons will give positive result for that
distance (the probability distribution function is not zero).
Clearly the result of such an experiment should not be inter-
preted in terms of the location of a discrete particle. To get
around this difficulty we frequently describe the electron in
an atom as an electron cloud.2 This description is more in-
tellectually satisfying than a particle description. It focuses
attention on the wave description of the electron and ignores
size or location which have almost no meaning in this con-
text.