Orbital Shape Representations

Osamu Kikuchi
The University of Tsukuba, Sakura, Ibaraki 305, Japan
Keizo Suzuki
Science University of Tokyo, Kagurazaka, Tokyo 162, Japan

Quantum chemistry has become important in the under- function of the atomic orbital. The radial function
Yim{9,<t>)
graduate education of chemistry students. Correspondingly, R„/(r) a constant, and the plot distance, d,
is chosen to be
physical chemistry textbooks contain various types of repre- varies with direction.
sentations of the electronic structure of atoms and chemical
d =
|Y/m(0,if>)|
bonds in molecules. Atomic and molecular orbitals are illus-
trated in several ways to help students understand orbital In the case of a two-dimensional polar plot of a 2px orbital
shapes. We wish to comment on orbital representations that the xy plane, where 90°, the diagram is ob-
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(Fig. 1(a)) on 9 =

have been proven beneficial in our lectures. tained by

Figure 1 shows several representations of the hydrogen 2px
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atomic orbital, p2Px, and its electron density distribution, OP CC

| COS01

In this case the plot distance OP is proportional to the func-

p2px
=
f?2p(r)YPx(fl,</>)
tion value at Q which is located along the OP direction and on
a circle of a given radius. The polar plot diagram of the density
R2P(r) =
(l/2\/6) exp(-r/2)r function of the 2px orbital, Figure 1(b), is obtained similarly
by
Ypx(0,0)
=
(-\/3/2 \/~?ij sinfl cos<f>
OP )cos<f>)2
A traditional way of illustrating atomic orbitals is by use of
two-dimensional polar plot representation of the angular The polar plot diagrams are not contour lines.

Figure 1. Hydrogen 2p„ atomic orbital and its electron density distribution, (a) Polar plot of p2Px on the xy plane. The OP distance is proportional to | cos<f> \. The positive
region means that cos<t> > 0 in this region, and the negative region means that cos<j> < 0 in this region, (b) Polar plot of (p2Pxf on the xy plane. The OP distance is
proportional to jcos0)2. (c) Contour lines of p2px on the xy plane. Solid lines were used for the positive function values and dotted lines for the negative function values.
The values cited are in units of a.u.-3'2. (d) Contour lines of (pzpx)2 on ,he *y plane. The values cited are in units of a.u.-3. (e) Pseudo-three-dimensional plot of p2Px-
The function values calculated on the xy plane were plotted along the z axis, (f) Three-dimensional contour surfaces of p2Px The solid-line surface corresponds to
p2Px
=
+0.01 a.u.-3'2, while the dotted-line one corresponds to p2px —0.01 a.u.-3,z.
~

206 Journal of Chemical Education

 Figure 1(c) is the linear contour map of \p2Px on the xy plane, Hybrid atomic orbitals are also represented by polar plots
and Figure 1(d) is the corresponding density function, \4>2px\2- in textbooks. When the sp hybridization is considered be-
To obtain these contour diagrams, the function values were tween \p2px and i/to,
calculated at (131 X 161) points on the xy plane, and the
contour line for a given value was drawn by interpolation. *p2s
=
R2s(r)Ys(0,0)
Figure 1(e) is the pseudo-three-dimensional plot of \p2Px in R&Jr) =
(l/2\/2) exp(-r/2)(2 -r)
which the function values on the xy plane are plotted along
the z axis. Although Figure 1(e) may be aesthetically more Ys(#,0) =
1/2%/rr
attractive than Figure 1(c), both involve almost the same in- the hybrid orbital ipsp cannot be expressed as a product of the
formation about the atomic orbital. radial function and angular function, since Ra„(r) is different
Three-dimensional contour surfaces are another way to il- from R2p(r).
lustrate atomic orbitals (Fig. 1(f) for the 2P* orbital). Figure
1(f) was obtained by successive contour line drawings on 'PsP
=
+ 4>2px) +* R.,p(r)Ysp(#,0)
several planes that are parallel to the xy or xz plane. The
solid-line surface indicates 1p2Px = +0.01 a.u._3/2, while the Thus, it is impossible to represe :t the angular part of the
dotted-line one indicates \p2Px —0.01 a.u.-3''2. The three-
= hybrid orbital using a polar plot.1 Polar plots appearing in
dimensional contour surface may be the best represenation textbooks may be constructed using the plot distance
of the orbital shape. This method has been employed for the d =
|(l/vr2)(Ys + Yp,)|
molecular orbital representation of many organic molecules
by Jorgensen and Salem (1). and ignoring the different radial functions. It is possible to
The polar plot representation appears most frequently in justify this representation in the following way. If we use
current physical chemistry textbooks. The polar plot diagrams Slater-type orbitals, x
(Fig. 1(a) and 1(b)) illustrate the angular dependence of the X2s =
l(2/v/3)f5/2 exp(—frlrjSl^Viri
atomic orbital and the density function. However, we must
emphasize and elucidate in our lectures how these diagrams X2Px
=
|(2/v/3)f6/2exp(-fr)rSI(\/3/2v/7r) sin# cos^l
are obtained; since many chemistry students are not familiar
with polar plot representations, they often mistake a curve
such as is given in Fig. 1(a) or 1(b) for a contour line. In order
1
This does not mean that it is impossible to represent the hybrid
to explain the electron density distribution of the atomic or- orbital using a polar plot. For a fixed vaiue of r, the hybrid orbital is a
function ot d and 4>, *PsP = a + bYPx, where a and bare constants whose
bital, we explicitly tell students that the electron density values depends on r. Thus the polar plot is possible for d « | a + bYPx |.
distribution is obtained from the polar plot diagram (Fig. 1(b)) The shape of the polar plot changes depending on the value of r chosen.
by multiplying the square of the radial function, (R2i(r)]2. In this sense, the polar plot is more difficult to interpret and explain, but
Nevertheless, it is difficult for students to conceptualize conceptually it is not impossible. We acknowledge the comments of
electron density distribution by this statement. a referee on this point.

4f5z3-3zr2 z 4^5yz2-yr!
Z

4^x3-3xy2 4f
zx -zy‘

(d) (e) (g)

Figure 2. Three-dimensional contour surfaces of seven 4t atomic orbitals of the hydrogen atom. The contour surfaces correspond to \p +0.005 a.u.~3/s (solid lines
~

surface) or = —0 005 a.u-3/2 (dotted lines surface).

Volume 62 Number 3 March 1985 207

where f is the orbital exponent, the sp hybrid orbital can be
represented by a polar plot since the two radial functions are
the same. However, even if the Slater-type orbitals are used,
the polar plot cannot be employed without an approximation
for the hybrid orbitals involving s, p, and d orbitals. In the
dsp2 hybrid orbital, for example,
(X3d*2-y2 + X4s +
=
PdspZ V"2X4pJ
V2
the orbital exponent and function form of the radial part of
the 3dx2-y2 orbital are different from those of the 4s and 4p
orbitals. An approximation is required for the polar plot
representation of the dsp2 hybrid orbital (2). In addition, a
polar plot cannot be used for a correct representation of the
molecular orbital, since the molecular orbitals consist of
atomic orbitals at different centers.
For the reasons described above, polar plots are not ap-
propriate for atomic and molecular orbital representations.
Based upon our experiences, polar plots have no teaching ef-
fectiveness and should be omitted from lecture presenta-
tions.
The contour line representation of an atomic orbital, p,
involves the electron distribution, p2, since representations
Figure 3. Contour-line maps of the 4f orbitals on specific planes, (a) 4%z3_3z/£ on the xz plane, (b) 4f5xz2-x/2 on the
or 4/y3_3yx2 on the xy plane, (d) 4 fxyz or 4 fzxi-zyi on the plane which is parallel to the xy plane and z = 10 a.u.
208 Journal of Chemical Education
for both p and p2 have exactly the same line shape, as shown
in Figures 1(c) and 1(d). These figures show the angular de-
pendence of the electron density distribution clearly and no
further explanations are necessary when it is applied to hybrid
atomic orbitals and molecular orbitals. It is obvious that the
contour line representation is better than the polar plot
model.
Graphing contour line diagrams of atomic and molecular
orbitals on a given plane is now very easy (3-7). A universal
type of graphics display can be employed even for illustration
of three-dimensional contour surfaces as shown in Fig. 1(f).2
The three-dimensional contour surface may be the best rep-
resentation for helping students to acquire a general grasp of
orbital shape. A shortcoming of this representation is that it
involves no information about the electron density distribu-
tion inside the contour surfaces. Thus, a combination of
contour lines diagrams on a specific plane and a three-di-
mensional contour surface representation may be used ef-
2 All
figures presented here were drawn on the low-resolution
graphics display terminal with 512 X 460 dots.
xz plane or 4f$y2z-y,2 on the yz plane, (c) 4fx3_3xy2
fectively for correct understanding of atomic and molecular Acknowledgment
orbitals. Figures 2 and 3 are examples of this combination of The authors are very grateful to A. J. Hopfinger for his
drawings, where seven 4f atomic orbitals of hydrogen are many helpful suggestions.
shown.

'I'ifw-M =
(1/3072^) exp(-r/4)z(5z2 -

3r2)
=
(l/1024V30vr) exp(-r/4)x(5z2 -
r2)
Literature Cited
=
(1/1024V307T) exp(-r/4)y(5z2 r2)
-

,2-yr2 (1) Jorgensen, W. L., and Salem, L., “The Organic Chemist’s Book of Orbitals,” Academic
Press, New York, 1973.
'Py,x2-zy2
=
(1/1024x/Iir exp(—r/4)z(x2 -

y2) (2) Cohen, I., and Del Bene, J., J. CHEM. EDUC., 46, 487 (1969).
(3) Bader, M., J. Chem. Educ., 48,175 (1971).
'Pilzyz
=
(l/512i/3ir) exp(-r/4)xyz (4) Craig, N, C., Sherertz, D. D., Carlton, T. S., and Ackermann, M. N., J. Chem. EDUC.,
48,310(1971).
(l/3072-v/2x) exp(-r/4)x(x2 3y2)
~ -

'l'Vx3-3xy2 (5) Holmgren, S. L., and Evans, J. S., J. CHEM. Educ., 51,189 (1974).
(6) Scaife, D. B., J. CHEM. Educ., 55,442 (1978).
'Pify3-3y,2
=
(l/3072/\/27r) exp(—r/4)y(y2 -

3x2) (7) David, C. W., J. CHEM. EDUC., 58, 377 (1981).

Volume 62 Number 3 March 1985 209