Arno Liberles

Fairieigh Dickinson University

Teaneck. New Jersey 07666

A great many quantum mechanical concepts are included

in modern introductorv organic chemistrv courses: vet because
the course is frequently kmmathemaiical, the& ideas are
discussed qualitatively and, as a result, less precisely. Consequently, the student may end up with an inaccurate mental
picture of what is actually being described. Such an initial
misconception can he difficult to correct a t a later stage in the
student's development, and it seems worthwhile to spend
some extra time to ensure a proper initial understanding.
One important concept is that of delocalization. When does
it take place; what is a suitable measure of delocalization; and
what about it imparts stability?
Delocalization
The idea of delocalization, which is now well-rooted in the
jargon of organic chemistry, results from the popularity of the
Hiickel approach to molecular-orbital theory with its calculation of delocalization energies as a measure of stahility (1-4).
Since the original Hiickel method applied only tom-systems,
the student is sometimes led to believe that only these electrons are delocalized. However in molecular orhital theory
delocalization is not so restricted, and the a as well as the
"nonhonding" or "lone-pair" electrons are also delocalized.
All electrons are delocalized in the sense that all molecular
orbitals can involve atomic orhitals from every nuclear center.
In a planar system such as benzene, there are a- and a-type
molecular orhitals, and while hoth types are delocalized, they
do not mix. However, if the system does not contain the proper
vlane of svmmetw.
". even a-a sevaration is not mathematicallv
possible. In such cases, while the molecule may contain a
double bond in the classic sense, no molecular orhitals can he
considered as just a or m. ~ e p e n d i on
n ~the system, a-m mixing
may he slight, or there may he nothing resembling a r-molecular orbital. Examples are propene in the 30' methyl-rotated
geometry (I),cvclohexene (II), and other alkenes, ketones, etc.
not having the necessary plane of reflection.

In the linear combination of atomic orhitals appro1

(LCAO), a molecular orhital JIR takes the form
=

Propene in the 30"-geometry (I) is neither a reactant nor

a transition state. However, this geometrvdoes illustrate the
idea of n-n mixing, and in Table 1 we present $ 1 2 for the system.' The y,z -plnne contains the cnrhon atoms, and the molecular orbital is ddinitrlv n n - t-.
v w with lnree coefficients
-~~~~~~~
multiplying p,~,and p,z. Yet a-mixing does take place, not
only in the hyperconjugative sense, hut also involving the 2s,
2py, and 2pz orhitals on the carbon atoms as well as the 1s
orhitals on the olefinic hvdroeens.
In cvclohexene the a - m
.
mixing is much greater, and for systems such as cyclooctatetraene nothine" resemhline a classic a-molecular orhital can
he found.
The concevt of a-delocalization is not generallv introduced
in the early ;tages of an introductory organic colrse because
it is not necessary to do so in order to explain the behavior of
most organic molecules. Thus the student may he left with the
impression that r-electrons are only sometimes delocalized
and that o-electrons almost never are. Since this is incorrect,
it may well he worthwhile to point out that o and nonbonded
electrons are also delocalized over the entire system but that
one need not frequently invoke this fact in order to explain
the behavior of the molecules.
Since all electrons are delocalized, one needs a suitable
criterion to determine whether, in fact, such delocalization
lowers the energy. Based on the "particle-in-a-box" problem,
the expectation value of the kinetic energy operator T would
seem to fulfill this requirement. It is not meant to imply that
a auantum mechanical calculation is necessarv in order to
d i s k delocalization; it simply means that delocalization can
be associated with changes in the kinetic energy of a system.
If the number of nodes in the wavefunction does not increase,
greater delocalization lowers the kinetic energy of the system;
the
more localization raises it. If the number of nodes
wavefunction does increase, then even increased delocalization
can he accompanied by an increase in the kinetic energy of the
system.
Of course, for real systems, one could equally well use the
potential energy of the system since these two quantities are
related hoth by the virial theorem and by summing, to the
total energy. Employment of the virial theorem, however,
leads to some interesting conclusions.
Reactants, intermediates, products, and transition states
are all stationarv states: that is. thev renresent ~ o i n t on
s the
electronic energy surface where ~ E ? ~ R ' (isRa shuctural parameter) is zero. For such points, the virial theorem relating
~

~~

x aikmi

where the 4; are atomic orbitals generally centered a t a nucleus.

Table 1.
C1

Delocalization

'The molecular orbitals are the result of single determinantal abinitio SCF calculations using the 3G basis set. See Ref: ( 1 5 ) .

The Coefficientr for $ , , o f Propene in the 3OD6eometry

C2

<

C3

Volume 54, Number 8. August 1977 / 479

must still increase. A decrease in the potential energy leads

kinetic, potential, and total energies takes the particularly

simple form given by eqn. (1) (5)

to stahility.

where E is the total energy, T the kinetic energy, and V the

potential energy of the system. For two different stationary
states

Since all of the electrons in a molecule are delocalized, the

idea of localized lone pairs in nonbonding orbitals is an oversimplification. However, the idea is so familiar and explains
so much of the chemistry of heteroatoms that it may be
worthwhile to examine the concept in more detail. Thus, the
structure of formaldehyde is written classically as

From (2), we see that AE = -AT, and a process that lowers

the kinetic energy actually causes an increase in the total energy of the system. Only an increase in the magnitude (lowering) of the potential energy reduces the total energy and
gives rise to stabilization. Therefore, in a reaction, if one ;s to
attribute enhanced stahility of transition states, intermediates, products, or reactants to delocalization, this favorable
effect must he due to a more favorable potential energy situation.
Consider, a s a case in point, covalent-bond formation from
two atoms or radicals
R. + R.'

R - R'

Since the process is favorable, AE is negative. Consequently,

the change in the kisetic energy, AT, for the process must be
oositive and unfavorable. In the case of two hvdroeen
. .. atoms.
for rxnmplv, hond formntion iiartually n Iwalvation process.
The two electrons are more lhralized in the hvdroren molecule
than they are in the separated atoms. ~ d o nt h does each
electron interact with the other nucleus, it also interacts more
strongly with its own nucleus. In a mathematical sense this
is reflected in an increase in the orhital exponent of the hydrogen 1s orbitals during hond formation. This increased
exponent shrinks the size of the orbitals, increases the kinetic
energy of the electrons hut also increases the magnitude of the
potential energy; enhanced stahility results.
Bond formation in the hydrogen molecule localizes the
electrons and leads to an increase in the kinetic energy of the
system; yet the potential energy becomes more negative, and
the latter effect imparts stahility to the molecule (6).
Heitler and London ( 7 ) in their classic treatment of the
hydrogrn molrcule did nor nlter the whirnl exponent of the
Is orhtnle, and whilt: their calrulnted enerrv
. .. for bond formatim is quire y<,ud,n reduction in the kmetirenergy srems
tu he resp~~nsil~lr.
Later work iw Wanp ( 8 , and b y Rosen (91
incorporates the necessary adj&ahlebaramete;and
attrih:
utes covalent-bond formation correctly to a more favorable
potential energy.
For larger systems, such as the combination of two methyl
radicals to form ethane, the electronic kinetic energy must still
be greater in ethane than in the two methyl radicals. The virial
theorem requires that covalent-bond formation always he
accompanied by an increase in kinetic energy. A lowering of
the potential energy causes bond formation to he favorable.
If one partitions the potential energy change into components
where AV,. represents the change in nuclear-electronic attraction during covalent-bond formation from the separated
atoms or radicals. AV.,.. the chanre in electron-electron repulsions, nnd A \ ' , , , rhe t.hnngr ill nuclear-nu<learrepulsiun.;,
then rovnlent-lmnd formation i i due I\'.
becominr! more
negative; AVe, and AV,. will generally be Gsitive andunfavorable (10, 11).
The concept of delocalization can he used to explain stability, hut the greater stability of one chemical entity relative
to another cannot be due to more favorable kinetic energy
situation. It must he due to a more negative potential energy
in the more stable system. For example, when two methyl
radicals combine to form ethane, even though the electrons
are now delocalized over the larger system their kinetic energy

Hi"H
'

with two pairs of nonhonded electrons. The molecular orbitals

of the molecule are (with the x,y-plane a s the molecular
plane)'
$1 = 150
$2 = L C
$3 = -0.12 ( 1 s ~=
) 0.28 (%c) + 0.16 ( p d - 0.22 (lso) +
0.77 (%o) - 0.17 ( p a d
$1 = -0.18 (lsc) + 0.57 ( 2 s ~) 0.23 (p,c) + 0.10 (lso) 0.43 ( 2 ~ 0 ) 0.16 (pZo)+ 0.27 (sH1)+ 0.27 (SHZ)
$5 = +0.54 (P,c) + 0.42 (p,o) = 0.31 ( S H ~ 0.31 (SHZ)
$6 = -0.11 (23~)
- 0.45 (pIC) + 0.50 @SO) + 0.68 (pzO)+
0.16 (SHI) + 0.16 (SHZ)
$7 = +0.61 (pvc)+ 0.67 (pya)
$8 = +0.17 (p,c) - 0.88 (p,o) + 0.35 ( S H ~ 0.35 ( s m )
One sees clear evidence of o-delocalization, and although
$a because of the large coefficient multiplying p,o, can be
considered in a rough way as containing one of the "nonbonded" pairs, the other pair must occupy !be,which the 3G
calculation places below the *-molecular orhital and which
It is possible, of
is even more effectively delocalized than
course. to carrv out unitarv transformations on the molecular
orhitals whicb, to some degree, localize them, but total localization is never possible. Dewar and Worley have shown that
for acetone and hexafluoroacetone it takes considerably more
energy to remove an electron in the latter molecule from what
would classically be called a nonbonded localized orbital on
oxygen (12).
Although "nonhonded" and o-electrons are not truly localized, this picture predicts correctly the behavior of carbonyl
compounds in a wide variety of reactions and is certainly the
easiest way to explain their chemistry. I t seems worthwhile
though to indicate somewhere in the organic chemistry course
that this approach is an approximation.

480 / Journal of Chemical Education

L q d*
Figure 1. Total electronic density diagram for non-bonded pairs.

- . ..

Figure 2. Top view of d i a p r n In Figure 1,

The water molecule represents another interesting example.

The structure is usually written as

The f i t integral inside the brackets in eqn. (3) is the dipole

moment of an electron in apures orbital while the last is that
of an electron in a purep. We know these to be zero since there
is no dipole moment associated with pure s and p orbitals.
Therefore. the diwle moment associated with the hvbrid must
come from the cioss-term. Furthermore, the maximum value
d e ~ e n dnot
s on the internal.
,. . which is constant for all hvbrids.
hut on the value of A. We m u t simply maximize the function
X/I
. .1 h") tn find whirh tvuc
". of hvhrid has assoriated with it
the maximum dipole moment.
We take the derivative and equate it to zero
~

.~

with the "nonbonded" electrons assumed to occupy slightly

modified sp3 hyhrids. These, very approximately, look as
follows

c+/"
H'

This picture leads to the expectation of a bimodal electronic

distribution; yet a picture of the total electronic density in the
plane of the "nonbonded" pairs has been published and actually appears as shown in Figure 1 or, alternatively, as in
Figure 2 (13).There is no bimodal distribution.
This result also has interesting ramifications for molecules
like methanol which exist in the geometry (14)

The electron has a maximum dipole moment when occupying a hybridized nonbondingorhital having A equal to f1,
and these correspond to the two s p hyhrids. I t may be of interest togive the values of thequantity U ( 1 + A2) for the more
common values of A, and we do that in Tahle 2.
The last value in
Tahle 2 is obtained
Table 2. TheValuesaf hl(1 + A 2 ) for
either by using
s, sp, sp', sp: and p orbitals
L'HBpital's rule or
by rewriting the
"('
+
quantity as I/(X
1/X) and letting A
approach infinity.
3%
0.433
Starting with pure s
orbital, mixing in p
character brings
about a rapid increase in the dipole moment. The average position of the
electron moves away from the nucleus. The maximum occurs
when equal amounts of s and p have been mixed. Continued
increase i n p character gradually reduces the dipole moment
back to zero. It may come as a surprise that the maximum
moment is associated with the s p hybrid rather than the sp3.
This result and some of those stemmine- from delocalization
arguments indicate that even our most basic assumptions
should continuallv he reexamined. For example, do the six
r-electrons in beizene really acruunt for its s ~ n h i l i tor
~ ,arr
the 36 o-electrons actuallv responsible (If?)? Even tndnv, this
cannot he answered with cervery fundamental
tainty.

"'

).
.o'

H
If one uses the localized picture for the nonbonding pairs,
this structure corresponds to a completely staggered conformation with a carbon-hydrogen hond in the region between
the lone-pairs on the oxygen atom, but this satisfying picture
is lost if one uses a more accurate description such as the one
just presented for water.
The pictures we present in the introductory organic
chemistry courses a m both simple and appealing and generally
lead to correct predictions ahout the behavior of organic systems. Nevertheless, they do not hold up under rigorous scrutiny.
The idea of localized lone pairs in nonbonded hybridized
orbitals is so well ingrained and works so successfully that it
seems worthwhile to examine more closely some of the predictions of this approach, for even here the conclusions are not
obvious. Consider, for example, which type of nonhonded
hybrid-sp, sp2, sp3-gives rise to the largest dipole moment.
A hybridized nonbonding orbital h can be written as2
h = (1 + h2)-'" ( S + Ap)
where A takes on the values 3lf2, 2112,and 1for the common
sp" sp2, and s p hybrids. The dipole moment p of an electron
in such a nonbonded hybrid is
p = jhedhdu
where e is the electronic charge and d its distance from the
nuclear center.
Subsituting for h and expanding leads to
p =

1 t A

J(s

+ Ap)ed(s + Apldu

2This derivation was presented by Dr. Ruben Pauncz at the

Quantum Chemistry Institute given at the University of Florida,
Gainesville, in January 1969.

Conclusion
The ideas iust oresented are neither verv difficult nor very
mathematical, A d their introduction -into the organic
chemistry course would not take much time. They may give
the student a better idea of some fundamental concepts.
All electrons are delocalized, and such delocalization, if it
is truly to account for the difference in energy between stationarv states. must result in a lowerinn of the potential energy. The kinetic energy must increase with increased stahility
of the svstem. Alternatively, certain processes, considered to
he del&alizations, may actually bd localizations, e.g., the
formation of the covalent hond in the hydrogen molecule.
Even then, the kinetic energy must increase, and greater
stability must come from a lowering of the potential energY.

Acknowledgment
This work was done a t the Universitv of California.
Berkeley.
The author is verv much indebted to the Facultv of the
Chemistry ~ e ~ a r t m e na t the University of ~aiifornia,
Volume 54, Number 8. August 1977 1 481

Berkeley, and especially to Professor A. Streitwieser, Jr., for

the gracious hospitality extended to him during a Sabbatical
year spent there as Visiting Professor.
Literature Cited
(1) Liberles, A , "lntrdudion toMolecular-Orhitel Theary,"Holt. New York, 1968.
Chhmiitryl.. M
~
~N~~ y~Y Y ~
k
I
(2) Liberlea, A . , - I ~ ~ toThhhhtiti~
& ~ ~ ~ ~Ma,,ii
~
1968.
(3) Streitwieser, Jr., A , '~MoleeularOrbital meom
for organic chemkte," wil*, ka.
York. 1961.
(4) Roberta, J. D.. '"Notes on M o l ~ u l a rOrhitel Cslculations: Benjamin, New York,
1961.

482 1 J w ~oflChemical Education

;I 2:;.~:~&~~,"~;a

Hill,Nw
~ o r k 1963,
.
Chapter 3.
(7) ~ e i t l e rw.,
, and h n d o n , F,z ~ h y s i k 44.4%
,
(19271.
(81 Wsng, S. C., Phys Rau. 31.579 (1928).
(9) Rosen, N., Phyr. Re".. 38,2099 (19311.
(10) Eile.8, J. E.. and Liberlr*. A,, J , Arne?. Chem Soc., 97,4183 (19751.
(11) Liberles.A.,Greenherg,A..and Eilers, J.E., J.CHEM. EDUC.,60,676 (19731.
(12) Dewar, M. J. S., and Wor1ey.S. D., J. Chem. Phys, 50,654 (19691.
(13)
figurea are taken from Streifwieser, h.,A,, and Owens. P. H., "Orbital and
~ These
,
Electron Density Disgrsms," Maemillsn, New York. 1973. p. 123.
(14) Ivash, E. V.,and Dennisan, D. M . , J Chem. P k m 21.1804 U953).
(15) Hehre, W. J., Stewart, R. F.,snd Pople, J. A., J. Chem. Phys. 51.2657 (1969).
(16) Wiherg, K. B.. " P h y s i d Olganic Chemistry," John Wileyand Sons.lne.. New York,
1964, p. 66 (seefootnote 23 therein).