Article

pubs.acs.org/jchemeduc

Construction of Ligand Group Orbitals for Polyatomics and

Transition-Metal Complexes Using an Intuitive Symmetry-Based
Approach
Adam R. Johnson*
Department of Chemistry, Harvey Mudd College, Claremont, California 91711, United States
*
S Supporting Information

ABSTRACT: A molecular orbital (MO) diagram, especially its

frontier orbitals, explains the bonding and reactivity for a chemical
compound. It is therefore important for students to learn how to
construct one. The traditional methods used to derive these diagrams
rely on linear algebra techniques to combine ligand orbitals into
symmetry-adapted linear combinations or ligand group orbitals
(LGOs). Over the past 10 years, I have developed and refined a
simple graphical method for generating ligand group orbitals. The
method is an extension of concepts that the students already know
from general chemistry: VSEPR and valence bond theory, which are
then used to create a generator function. LGOs are prepared by
matching symmetry (nodes and phase behavior) of the generator
function. The LGOs generated by this technique are qualitatively
correct and sufficient for the “back-of-the-envelope” MO diagrams for which they are intended. Through a series of in-class group
work and out-of-class problem sets, students learn to derive LGOs for main-group, organometallic, and coordination complexes
quickly and correctly.
KEYWORDS: Upper-Division Undergraduate, Inorganic Chemistry, Group Theory/Symmetry, MO Theory

M olecular orbital (MO) theory is an excellent conceptual

model for the bonding in molecules. With ever-
improving computer processors, modern density functional
form the MO diagram. For polyatomics, one must consider
each atom interacting with all of the other atoms, resulting in a
multicomponent problem.4 As a result, inorganic molecules are
theory,1 and software packages such as Gaussian2 or Spartan,3 it often not treated as rigorously as they should be.
has become straightforward to do high-level calculations on In my inorganic chemistry course, I have developed a
complex molecules even in the undergraduate curriculum. qualitative, symmetry-based derivation of LGOs that is then
However, due to this emphasis on computers, students are used to construct the corresponding MO diagrams. A major
often unable to make “back-of-the-envelope” type predictions goal of the technique is that it is rapid and easy to apply to a
when presented with a new molecule in a seminar or during new molecule, especially for transition-metal complexes. The
their research. This simple and rough MO theory is used by course usually consists of about 15−20 upper-level under-
many practicing inorganic, organic, and organometallic graduate students. Physical chemistry (including symmetry and
chemists to quickly get an estimate of the frontier orbitals so group theory) is a co-requisite for the course, but most of the
they can predict, interpret, or rationalize chemical reactivity and students take it the previous year. The course meets in three, 50
bonding. In addition, students are often unable to interpret min sections per week; two of the meetings are traditional
their computational results, especially for coordination lectures, while the third involves small-group problem work
complexes, because they do not know what they are looking with in-class presentations of solutions. The major student-
for at the frontier energy level.
learning goal is for them to be able to quickly draw a reasonably
Students typically study MO theory in the introductory and
accurate (in terms of relative energies of the frontier orbitals)
physical chemistry curricula, though a detailed description of
MO diagram for a transition-metal complex of known or
the theory is usually limited to diatomic molecules. Making the
jump to more complicated molecules, such as polyatomic main- predicted geometry. The students are told that this level of
group compounds or transition-metal complexes, requires the theory is not sufficient for “geometry optimizations” such as
explicit consideration of symmetry and group theory for the those performed by computational packages, but it does allow
formation of symmetry adapted linear combinations (SALCs), for rationalization and prediction of chemical reactivity given an
also called ligand group orbitals (LGOs). This is often a input geometry.
difficult task for beginning students. For diatomics, one has
only to consider the two component atoms that interact to
© XXXX American Chemical Society and
Division of Chemical Education, Inc. A dx.doi.org/10.1021/ed300115t | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

The technique described herein is based on that published by Table 1. Electronic and Molecular Geometries,14 and
Verkade,5 but it has been simplified and made more Valence Bond Hybrid Orbitals for Main-Group Compounds
approachable for students beginning their study of MO theory. with Increasing Number of Electron Groups around the
The textbook by Purcell describes an approach to forming MO Central Atom (n)
diagrams using a similar symmetry-based technique.6 The
n Electronic Geometry14 Molecular Geometry Hybrid Orbitals
technique builds steadily through a variety of bonding models
that students have seen in prior courses. Beginning with the 2 linear (D∞h) linear (D∞h) spz
Lewis structure and an appropriate VSEPR geometry, the 3 trigonal planar (D3h) trigonal planar (D3h) sp2 (s, px, py)
LGOs are derived based on concepts from valence-bond bent (C2v)
theory. Students are quite confident in their abilities by the end 4 tetrahedral (Td) Tetrahedral (Td) sp3
of this four to five week process, which provides an MO trigonal pyramidal
(C3v)
foundation for the rest of the term. Students can describe the
bent (C2v)
bonding of complicated molecules with a good understanding
4 Square planara (D4h) square planar (D4h) dsp2 (dx2−y2)
of not only the molecular nature of the orbitals, but also of the 5 trigonal bipyramidal trigonal bipyramidal dsp3 (dz2)
reactivity of a main-group compound or transition-metal (D3h) (D3h)
complex.

■
seesaw (C2v)
t-shape (C2v)
PART 1. BACKGROUND AND THE FOUNDATION linear (D∞h)
OF THE METHOD 5 square pyramidala square pyramidal (C4v) dsp3 (dz2)
(C4v)
Students typically learn Lewis structures and VSEPR in the
6 octahedral (Oh) Octahedral (Oh) d2sp3 (dz2, dx2−y2)
first-year chemistry course and subsequently learn to deal with
square pyramidal (C4v)
more complex bonding models in physical chemistry courses
square planar (D4h)
and more complex structures in organic chemistry courses.
6 trigonal prismatica trigonal prismatic (C3v) d2sp3 (dxz, dyz)
Lewis theory and VSEPR are reviewed, focusing on the (C3v)
breakdown of the theory for even simple molecules such as CO 7a pentagonal bipyramidal pentagonal bipyramidal d3sp3 (dx2−y2, dxy)
and O2,7 giving a rationale for continued work on MO theory. (D5h) (D5h)
Lewis theory is described as useful to explain bonding, but that 8a square antiprism (D4d) square antiprism (D4d) d4sp3 (dz2, dxy, dxz,
the simple theory does not always accurately predict chemical dyz)
a
behavior, requiring the use of more complex theories. Less common for main-group compounds, but useful to consider for
The MO diagram for H2+ is derived in detail using transition-metal complexes.
conventional quantum mechanical arguments. The wave
function describing the bonding molecular orbital is shown to two aspects of the character table are needed: the Mulliken
be identical to that obtained from valence bond theory.8 symmetry labels, used simply as labels for orbitals, and the
However, an important distinction in MO theory is the functions, which are needed for the formation of LGOs. Most
introduction of antibonding orbitals. By including the inorganic textbooks introduce symmetry and character tables in
antibonding orbitals, the bonding in O2 and CO can be more sufficient detail for the use of this method;15−17 more advanced
accurately described. However, to describe the bonding in texts are available for students with interest.18−23
polyatomics, the simple interactions of atoms cannot be readily
applied, and the use of symmetry and group theory is necessary. Generation of LGOs for Polyatomics
Terms (found in most general or inorganic chemistry The most important and conceptually most difficult aspect of
textbooks)9−13 that students will use and apply for the forming an MO diagram for a polyatomic is deciding what
construction of LGOs include the basic principles of VSEPR: groups of orbitals will interact. For a diatomic, a single atom
molecular and electronic geometries,14 spn valence bond hybrid interacts with only another single atom, and the MO diagram
orbitals, the parent geometries for MLn molecules (n = 2−6, can be constructed directly from the two components. For
Table 1), and deviations from the ideal based on lone pair or polyatomics, a single central atom interacts with all of the
bonding pair repulsions. The less common dmspn valence bond ligand atoms at once, resulting in a multicomponent problem.
hybrids are not available in some textbooks and are required for The problem is typically simplified using symmetry; the ligands
some geometries (for example dz2 sp3 for trigonal bipyramidal are arranged into symmetrical groups (symmetry adapted linear
geometry). Thus, a version of Table 1 is provided for student combinations). The concept is relatively easy to apply to the σ-
use. bonding interactions in main-group binary compounds such as

■ PART 2. APPLICATION OF TECHNIQUE TO

POLYATOMICS
BH3, SiCl4, PF6 or SF4; π-bonding is either treated separately or
ignored. Hydrogen ligand atoms use their 1s orbitals for σ-
bonding, whereas nonhydrogen ligand atoms are modeled to
have a single lobe pointed at the central atom (easily modeled
Symmetry and Group Theory as an spn hybrid orbital). Graphical combinations of the
To describe the bonding in polyatomic molecules, symmetry bonding lobes are then created that match the symmetry of a
and group theoretical considerations are usually used to reduce derived generator function24 using nodal features to guide their
the multicomponent problem to a two-component problem. formation using the following process outlined in Table 2.
Symmetry operations are introduced (as review for most of the The process is described as layering on techniques that the
students) at a level such that students are able to assign a point students already know. The student draws a Lewis structure
group to a molecule. Once assigned, the appropriate character and assigns its geometry from VSEPR. Then, they determine
table can be used to aid in the construction of the MO diagram. the point group of the molecule and the appropriate orbitals
For the purposes of the technique developed in this article, only that would be used from a valence bond approach. Next, the
B dx.doi.org/10.1021/ed300115t | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

Table 2. Process for Forming Ligand Group Orbitals

(LGOs)
Step Procedure
I Draw a Lewis structure and assign VSEPR geometrya
II Assign a point group to the molecular geometry
III Determine the VB hybrid orbitals for the electronic geometry of the
central atom
IV Use the VB hybrid orbitals as generator functions
V Generate the LGOs by combining the ligand σ-orbitals (lobes) to
obtain an orbital with the same symmetry as the generator function
VI Assign symmetry labels to the LGOs from the character table by
matching the label of the generator function
a
For transition-metal complexes, use the Kepert model (see below).

functions of these orbitals (found in the character table) are

used as generator functions to generate the LGOs, and finally, Figure 1. The a1′ and e′ generator functions and the resulting LGOs
symmetry labels are assigned. for bonding in BH3 in the D3h point group. This diagram emphasizes
The process is best seen with examples. The simplest case is phase and nodal properties of the generator functions and the resulting
a molecule without lone pairs, such as borane (BH3), where the LGOs with dotted lines and shading, respectively.
molecular and electronic geometries are the same. Because
there are three ligand hydrogen atoms, we need to generate as generator functions. For the current technique, it suffices to
three LGOs. The predicted VSEPR geometry (Table 1) is use those that overlap with the bonded atoms (the two
trigonal planar, in the D3h point group. The boron orbitals that hydrogens, in this case) to generate the LGOs. The remaining
would be used for bonding to the hydrogen atoms (using functions are used to predict the symmetry of the resulting lone
valence bond theory) are the sp2 hybrids derived from s, px, and pairs. For water, either the s or the pz can be used as one of the
py. Each orbital (or the corresponding function, [x2 + y2 + z2], generator functions as either can overlap with the ligand
and [x,y]) on the central atom is used as a generator function to hydrogens. Depending on the axis system chosen, either the px
generate an LGO with appropriate symmetry for bonding to or the py could be the second generator function (convention
the central atom. The LGO is generated by taking a linear places the molecule in the yz plane, though many texts use the
combination of the three hydrogen 1s orbitals on the ligand xz plane),18 while the other is used to predict the symmetry of
atoms. Contributions of positive, negative, or zero are chosen the second lone pair. The net result is that there are two lone
such that the resulting LGO has the same symmetry properties pairs and two LGOs.
as the generator function; this is done by inspection of the For students learning the technique, it is helpful to construct
phase and nodal properties of the generator function. a table or decision tree showing the interaction of the generator
For BH3, an LGO of a1′ symmetry can be generated from the functions with the molecule in question, as shown in Table 3.
s orbital on boron. Just as the generator function, this LGO will
have no nodes and will be all in-phase. It is obtained by Table 3. Interaction of Generator Functions with Ligands or
summing the three s orbitals on the three hydrogen atoms. Lone Pairs as a Tool for Assigning the Symmetries of the
Next, two LGOs with e′ symmetry can be generated from the LGOs in H2O (in yz plane)
px and py orbitals on boron. Using the py generator function
(with a node along the x axis), an LGO is obtained by summing Can Interact with:
two of the s orbitals in-phase and one of them out-of-phase; the Generator Function Symmetry Label Ligands Lone Pairs
node in the generator orbital is the same as the node in the s a1 yes yes
LGO. The third LGO is generated by the px generator function pz a1 yes yes
and both contain a node along the y axis. It is obtained by px b1 no yes
summing one s orbital out-of-phase with respect to a second; py b2 yes no
the third s orbital does not contribute to the LGO as it lies in
the nodal plane. The three resulting LGOs, shown in Figure 1,
have the same symmetry as the generator functions s, px, and Based on inspection of the table, for water lying in the yz plane,
py. From the D3h character table, s is a1′, whereas (x,y) is e′. A the px orbital must correspond to a lone pair, while the py
pencast demonstrating this procedure is available.25 orbital must correspond to a ligand group orbital. One each of
Dealing with lone pairs using this technique is slightly more the s and pz orbitals (for the current purpose, the decision is
complicated, and water is a good introductory example. arbitrary) corresponds to an LGO and a lone pair; the
Following the technique as above (Table 2), water is predicted symmetry of each is a1. The two resulting LGOs, shown in
to be bent, in the point group C2v. Water has four electron Figure 2, have the same symmetry as s and py. From the C2v
groups around it and its electronic geometry is tetrahedral; character table, s is a1 and py is b2.
however, with only two ligands, students will generate only two A final example, SF4, illustrates the case where the electronic
LGOs. The valence bond hybrid orbitals appropriate for geometry and molecular geometry of the molecule have
bonding in water are the sp3 hybrids, s, px, py, and pz, and two different axis systems. For this molecule, with nonhydrogen
of these orbitals will be used as generator functions to guide the ligands, we model the ligand atoms as having a lobe pointing
construction of LGOs. toward the central atom (a p or sp3 hybrid orbital in the case of
The complication for any molecule containing lone pairs is fluorine). The molecular geometry is see-saw with a C2v point
deciding which subset of the valence bond orbitals will be used group, but the molecule has a trigonal bipyramidal electronic
C dx.doi.org/10.1021/ed300115t | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

lone pair using this technique, but instead predict that a lone
pair of that symmetry will result when we construct the MO
diagram.
Many students with sufficient group theory backgrounds are
comfortable using the reducible representation technique for
the generation of LGOs, and students are encouraged to use
the technique if they wish. However, the mathematical
derivation of the LGOs often detracts from the simplicity and
rapidity of the graphical method. Several other examples of
LGO formation are given in the Supporting Information.

■ PART 3. APPLICATION OF TECHNIQUE TO

TRANSITION-METAL COMPLEXES
Applying the technique to transition-metal complexes is in
some ways easier than doing so for main-group compounds, as
there are generally no longer stereochemically active lone pairs
Figure 2. The a1, b1, and b2 generator functions, the two resulting to consider. The geometries of the complexes are predicted by
LGOs of a1 and b2 symmetry, and the predicted symmetries of the the Kepert model that considers only ligands,26 rather than
lone pairs (a1 and b1) for H2O in the C2v point group. VSEPR. The basic procedure is identical to that for main-group
complexes (Table 2): given the geometry, use the VB hybrid
geometry. Because valence bond theory predicts dsp3 hybrid- orbitals as generators for the LGOs. Three examples,
ization using the dz2 orbital (Table 1), the orbitals that are used [Fe(CN)6]4‑ in Oh, and [CoCl4]2‑ in both Td and D4h, illustrate
as generator functions are s, px, py, p,z, and dz2. To assign the the process.
symmetry of the resulting LGOs, use the VB hybrid orbitals In an octahedral complex, such as [Fe(CN)6]4‑, the
from the electronic geometry in the orientation of the molecular geometry is Oh, and valence bond theory predicts
molecular geometry (C2v in this example). The decision tree d2sp3 hybridization (Table 1). With six ligands, six LGOs are
for lone pair assignment for SF4 is given in Table 4; the px and required, and the s, px, py, pz, dz2, and dx2−y2 orbitals are used as
generator functions. It is simplest to assume that sp hybrid
Table 4. Interaction of Generator Functions with Ligands or orbitals on each cyano ligand point toward the central iron
Lone Pair as a Tool for Assigning the Symmetries of the atom. Combination of those six sp hybrid orbitals in an
LGOs in SF4 appropriate way by matching the phase and nodal properties of
Can Interact with:
the generator functions results in the expected LGOs with a1g,
t1u, and eg symmetry (Figure 4). The six LGOs thus
Generator Function Symmetry Label Ligands Lone Pairs constructed have the same symmetry as those of the six
s a1 yes yes generator functions (not shown).
pz a1 yes yes In a similar way, the LGOs for a tetrahedral complex,
px b1 yes no [CoCl4]2‑ can be derived. The four generator functions are s, px,
py b2 yes no py, and pz. In the Td point group; the x, y, and z axes point
dz2 a1 yes yes between the ligand dihedrals. Considering sp3 hybrid orbitals
on the four chlorines as the lobes pointing toward the central
py orbitals must be used to generate LGOs, while two of the atom, the four generator functions generate four LGOs with a1
three remaining a1 symmetry orbitals are used as generator and t2 symmetry (Figure 5).
functions. Two a1 LGOs are required for SF4, and it is arbitrary As a final example, the same cobalt complex could be
which two of the three a1 generator functions are used; for considered in the square planar geometry, with D4h symmetry.
simplicity, the s and pz generator functions are used to generate In this geometry, the generator functions are s, px, py, and dx2−y2.
the LGOs (Figure 3). Again, as the case for water, although the The resulting LGOs, with a1g, eu, and b1g symmetry are shown
symmetry of the lone pair is described, we do not generate a in Figure 6.

Figure 3. The 3 a1, b1, and b2 generator functions, the three resulting LGOs of a1 and b1 and b2 symmetry, and the predicted symmetries of the lone
pair (a1) for SF4 in the C2v point group.

D dx.doi.org/10.1021/ed300115t | J. Chem. Educ. XXXX, XXX, XXX−XXX

Journal of Chemical Education Article

LGOs for similar molecules. The tradeoff of reduced accuracy

in the bonding picture is made up for by the rapidity of the
derivation. The student can quickly predict the frontier orbital
set of a compound under study, and follow up with more
detailed calculations using a computer program if necessary.
Although the technique is easy to apply and useful for the
quick preparation of qualitatively correct MO diagrams, it is not
without flaws. First, although the procedure for selecting
generator functions for main-group compounds with lone pairs
works, students do not understand what it means to predict the
symmetry of a lone pair until later when we construct MO
diagrams.29 Students are shown the results from computations
on molecules such as water and SF4 to show them that their
predictions of lone pair symmetry are correct, even if the shape
Figure 4. LGOs of a1g, t1u, and eg symmetry, derived from s, (px, py, pz) of the lone pair is not familiar (see Supporting Information).
and (dx2−y2, dz2) generator functions for [Fe(CN)6]3‑ in the Oh point Second, the technique does not accurately predict the correct
group. “lobe size” for the e′ orbitals in BH3 and similar molecules.
Those students with interest can derive the correct coefficients
by recalling that the squares of the coefficients of the lobes sum
to unity. This is not necessary for a qualitative bonding picture,
and the lack of coefficients does not interfere with the ability to
generate LGOs with the correct symmetry and symmetry label.
Third, although π bonding can be successfully layered on top of
this technique, generation of π LGOs by this technique is not
straightforward. However, during construction of an MO
diagram, once σ bonding is “out of the way,” the orbitals left
on the ligands that can overlap with the central atom in a π
fashion are relatively easy to see. Fourth, the technique does
not address issues of orbital mixing (s−p, s−d, p−d) at the
central atom, although it could be readily modified to include
this idea (see Supporting Information for an example of
Figure 5. LGOs of a1 and t2 symmetry, derived from s, and (px, py, pz) including sp mixing in water). Finally, the focus of this
generator functions for [CoCl4]2‑ in the Td point group. technique is on its simplicity, and as such, it cannot be used
predictively. It is possible to generate LGOs for any structure,
even if it is not the lowest-energy geometry.
Early in the development of the technique, the terminology
of Verkade was used, and the generator functions were called
“generator orbitals”. However, this sometimes led to confusion.
Some students assumed that the central atom needed to have
the necessary orbital present in its valence shell to be used as a
generator. For example, in SF4 (Figure 3), students would not
always derive the correct LGOs. As the course emphasizes that
sulfur does not have valence d orbitals,30−33 students would
only consider generator orbitals based on s and p orbitals and
would either obtain three LGOs and a lone pair or four LGOs
and no lone pair. Similarly, in square planar methane (see
Supporting Information), students would only derive the three
Figure 6. LGOs of a1g, eu, and b1g symmetry, derived from s, px, py, and LGOs based on the s and p orbitals, neglecting to derive the
dx2−y2 generator functions for [CoCl4]2‑ in the D4h point group. fourth derived from the dz2 orbital. This student confusion has

■
largely gone away with the change in terminology.
In the interest of learning more about student performance,
PART 4. ASSESSMENT OF THE TECHNIQUE student learning was assessed over a multiyear period using the
After three weeks of lectures, in-class exercises,27 and several ACS standardized exam in inorganic chemistry. This exam is a
problem set questions, students are well-equipped to generate 60 question multiple choice exam given in a 100 min period.34
LGOs (and their corresponding MO diagrams) using this Questions related to MO theory (7 questions) were selected,
graphical approach. They generate LGOs for essentially any and the percentage correct in six student cohorts (Figure 7)
main-group, organometallic or coordination complex and was plotted. Because of the difficulty of the exam (39 correct is
almost all students are able to do so on examinations with in the 91st percentile) and the inexact match between the
little difficulty. A report from this Journal demonstrated the course and the standardized exam, a performance above 60%
construction of molecular orbital diagrams for molecules on a subsection of the ACS exam is considered to be acceptable
lacking a center of symmetry by using the fragment MO and a performance above 80% is superior.
approach and a traditional approach to forming LGOs.28 The molecular orbital theory topic, which was taught every
Students can apply the generator function technique to derive year, underwent significant revision and updating between 2001
E dx.doi.org/10.1021/ed300115t | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education Article

friend. I am indebted to my Chem 104 students, especially

those that asked probing questions as I developed the method.

■ REFERENCES
(1) Koch, W.; Holthausen, M. C. A Chemist’s Guide to Density
Functional Theory, 2nd ed.; Wiley-VCH: New York, 2001.
(2) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.;
Jr..; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.;
Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.;
Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi,
J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J.
B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R.
E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.;
Figure 7. Plot of student performance on the molecular orbital theory Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador,
questions on the ACS standardized exam (number of students by year: P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö .;
2001 (24), 2002 (17), 2003 (20), 2004 (10), 2005 (15), and 2011 Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09,
(16)). Revision A.1; Gaussian, Inc.: Wallingford, CT, 2009.
(3) Spartan ’10; Wavefunction, Inc.: Irvine, CA, 2010.
(4) Housecroft, C. E.; Sharpe, A. G. Inorganic Chemistry, 3rd ed.;
and 2003, but has remained essentially unchanged since that Pearson Education Limited: Harlow, U.K., 2008; p 122.
time. The performance by students on the molecular orbital (5) Verkade, J. G. A Pictorial Approach to Molecular Bonding and
theory portion of the exam showed steady improvement during Vibrations; Springer-Verlag: New York, 2002.
the years that the generator function method was developed, (6) Purcell, K. F.; Kotz, J. C. Inorganic Chemistry; Saunders College
rising to above 60% in 2003 and staying there through 2011. Publishing: Philadelphia, PA, 1977; pp 163−182.
The results show that the students have an acceptable (7) Following the rules for drawing Lewis structures, the best
structure for CO has only a double bond between the atoms (forming
understanding of MO theory using the methods described
the third bond breaks two common rules, requiring the formation of
herein.

■
formal charge from a neutral species and putting a positive formal
charge on oxygen, the more electronegative element). For O2, the
CONCLUSIONS Lewis structure predicts a diamagnetic ground state, whereas the true
The generator function technique is a simple and straightfor- ground state is a triplet diradical.
ward method for deriving LGOs and thus the MO diagrams, for (8) Karplus, M.; Porter, R. N. Atoms and Molecules; Benjamin/
main-group polyatomics and transition-metal complexes. The Cummings: Reading, MA, 1970; pp 304−305.
intuition gained by the techniques allows students to more (9) Housecroft, C. E.; Sharpe, A. G. Inorganic Chemistry, 3rd ed.;
deeply understand the results of high-level quantum chemical Pearson Education Limited: Harlow, U.K., 2008; pp 88−99.
calculations, but is easy enough to be drawn on the back of an (10) Miessler, G. L.; Tarr, D. A. Inorganic Chemistry, 4th ed.; Prentice
Hall: New York, 2011.
envelope. Students regularly derive quick MO diagrams during (11) Atkins, P.; Overton, T.; Rourke, J.; Weller, M.; Armstrong, F.
seminars, and several students have commented that this Shriver and Atkins’ Inorganic Chemistry, 5th ed.; Oxford University
approach made it easy for them to do so.

■
Press: Oxford, 2009.
(12) Oxtoby, D. W.; Gillis, H. P.; Campion, A. Principles of Modern
ASSOCIATED CONTENT Chemistry, 7th ed.; Thompson Brooks/Cole: Belmont, CA, 2012.
*
S Supporting Information (13) Laird, B. University Chemistry, McGraw-Hill: New York, 2009.
(14) The concept I call electronic geometry is defined differently by
Several additional examples of deriving LGOs using this
different authors and is sometimes called the shape of the electron
technique; an example of incorporating sp mixing at the central groups around the central atom or the electron group scaffolding
atom; several sample MO diagrams that illustrate lone pairs and predicted by VSEPR.
their symmetry prediction; graphical output from Gaussian (15) Shriver, D.; Atkins, P. Inorganic Chemistry, 3rd ed.; W. H.
calculations on water and SH4; a rough schedule showing how Freeman and Company: New York, 1999; pp 117−129.
the technique is staged; and a student handout. This material is (16) Housecroft, C. E.; Sharpe, A. G. Inorganic Chemistry, 3rd ed.;
available via the Internet at http://pubs.acs.org. Pearson Education Limited: Harlow, U.K., 2008.

■ AUTHOR INFORMATION
Corresponding Author
(17) Miessler, G. L.; Tarr, D. A. Inorganic Chemistry; Pearson
Prentice Hall: Upper Saddle River, NJ, 2004; pp 76−102.
(18) Cotton, F. A. Chemical Applications of Group Theory, 3rd ed.;
Wiley-Interscience: New York, 1990.
*E-mail: [email protected]. (19) Kettle, S. F. A. Symmetry and Structure, 2nd ed.; John Wiley and
Notes Sons: New York, 1995.
(20) Vincent, A. Molecular Symmetry and Group Theory, 2nd ed.; John
The authors declare no competing financial interest.

■
Wiley and Sons: New York, 2001.
(21) Carter, R. L. Molecular Symmetry and Group Theory, John Wiley
ACKNOWLEDGMENTS and Sons: New York, 1998.
My interest in MO theory and inorganic chemistry was sparked (22) Bishop, D. M. Group Theory and Chemistry; Dover: New York,
by Martin Ackermann, Oberlin College; he is a true mentor and 1973.

F dx.doi.org/10.1021/ed300115t | J. Chem. Educ. XXXX, XXX, XXX−XXX

Journal of Chemical Education Article

(23) Harris, D. C.; Bertolucci, M. D. Symmetry and Spectroscopy;

Dover: New York, 1978.
(24) Verkade calls these generator orbitals, a terminology which
students often find confusing, as described in the Assessment section.
(25) Johnson, A. R. Generating LGOs and constructing MO
diagramspencast. https://www.ionicviper.org/class-activity/
generating-lgos-and-constructing-mo-diagrams-pencast (accessed Oct
2012).
(26) Housecroft, C. E.; Sharpe, A. G. Inorganic Chemistry, 3rd ed.;
Pearson Education Limited: Harlow, U.K., 2008; pp 620−621.
(27) Johnson, A. R. Generating LGOs (SALCs). https://www.
ionicviper.org/class-activity/generating-lgos-salcs (accessed Oct 2012).
(28) Cass, M. E.; Hollingsworth, W. E. J. Chem. Educ. 2004, 81, 997−
1005.
(29) Calculated molecular orbitals for several molecules with lone
pairs are included in the Supporting Information.
(30) Burdett, J. K. Chemical Bonds: A Dialog; John Wiley & Sons:
New York, 1997.
(31) Mitchell, T. A.; Finocchio, D.; Kua, J. J. Chem. Educ. 2007, 84,
629.
(32) Coleman, W. F. J. Chem. Educ. 2010, 87, 999−910.
(33) Suidan, L.; Badenhoop, J. K.; Glendening, E. D.; Weinhold, F. J.
Chem. Educ. 1995, 72, 583−586.
(34) ACS − Division of Chemical Education − Examinations
Instutute − About Us. http://chemexams.chem.iastate.edu/about/
index.cfm (accessed Oct 2012).

G dx.doi.org/10.1021/ed300115t | J. Chem. Educ. XXXX, XXX, XXX−XXX