Topics
Hybridization of atomic
orbitals
Molecular orbital theory:
polyatomics
Application of character
tables
Delocalized bonding
5.1 Introduction
In Chapter 2, we considered three approaches to the bonding
in diatomic molecules:
Lewis structures;
‘¢ valence bond (VB) theory:
‘© molecular orbital (MO) theory
In this chapter we extend the discussion to polyatomic
molecules (ie. those containing three or more atoms)
Within the valence bond model, treatment of a molecule
XY, (n> 2) raises the question of compatibility (or not)
bbetwicen the positions of the Y atoms and the directional-
ities of the atomic orbitals on the central atom X. Although
fans atomic orbital is spherically symmetric, other atomic
orbitals possess directional properties (See Section 1.6)
Consider HO: Fig. 5.1 illustrates that, if the atoms of
the HO molecule lie in (for example) the yz plane, the
directionalties of the 2p, and 2p, atomic orbital of
‘oxygen are not compatible with the directioalities of the
two O-H bonds. Although we could define the 2 axis to
coincide with one O-H bond, the y axis could not (at
the same time) coincide with the other O-H. bond.
Hence, there is a problem in trying to derive a localized
‘bonding scheme in terms of an atomic orbital basis sot
(Gee Section 2.3). The next section describes a bonding
model within valence bond (VB) theory that overcomes
this problem. After we have considered how VB theory
views the bonding in a range of XY, species, we move
‘on to the problems of applying molecular orbital theory
to polyatomic species.
A polyatomic species contains three or more atoms.
polyatomic molecules
5.2 Valence bond theory: hybridization
of atomic orbitals
What is orbital hybridization?
‘The word ‘hybridization’ means ‘mixing’ and when used in
the context of atomic orbitals, it describes a way of deriving
spatially directed orbitals which may be used within VB
theory. Like all bonding theories, orbital hybridization is
4 model, and should not be taken to be a real phenomenon,
Hybrid orbitals may be formed by mixing the characters of
‘atomic orbitals that arc close in energy. The character of
hybrid orbital depends on the atomic orbitals involved and
their percentage contributions. The labels given to hybrid
orbitals reflect the contributing atomic orbitals, e.g. an sp
hhybrid possesses equal amounts of s and p ombital character.
Hybrid orbitals are generated by mixing the characters of
atomic orbitals,
"The reason for creating a set of hybrid orbitals is to
produce a convenient bonding scheme for a particular mole-
cular species. An individual hybrid orbital points along a
given internuclear axis within the framework of the
molecule under consideration, and use of a sot of hybrid
orbitals provides a bonding picture in terms of localized
o-bonds. In working through the rest of this section,
notice that each hybridization scheme for an atom X in a
molecule XY, is appropriate only for a particular shape,
the shape being defined by the number of attached groups,
and any lone pairs,
{A set of hybrid orbitals provides a bonding picture for a
‘molecule in terms of localized o- bonds 140 CHAPTER 5 © Bonding in polyatomic molecules
u 2», 2»,
Fig. 5.1 A comparison ofthe shape of the HO molecule (the
Framework of which is taken as lying in the yz plane) withthe spatial
properties ofthe 2s, 2p, and 2p, atomic orbitals of xygen.
@- +-©3-- —-3-
spbobit
®
G- --©93- — O-—
a phys
»
Fig. 5.2 The formation of two sp hybrid orbitals from one 2s atomic
‘orbital and one 2p atomic orbital
sp Hybridization: a scheme for linear species
‘The notation sp means that ones atomic orbital and one p
‘atomic orbital mix to form a set of two hybrid orbitals with
different directional properties.
4
Be(Z=4)
One possible combination of a 2s atomic orbital and 2p,
atomic orbital is shown in Fig. 5.2a, In the figure, the
colour of the orbital lobe corresponds to a particular phase
(Gee Section 1.6) and the addition of the 2s component
reinforces one lobe of the 2p, atomic orbital but diminishes
the other. Equation 5.1 represents the combination mathema.
tically. The wavefunction Wpiyaay describes a normalized
(Gee Section 2.2) sp hybrid orbital which possesses SO% s
and 50% p characte. Although eq, 5.1 and Fig. 52a refer to
the combination of 2s and 2p, atomic orbitals this could just
a well be 2s with 2p, or 2p., oF 3s wilh 3p,, and So on.
1 ty (
= pln tn) (5)
Now comes an important general rule: if we begin with n
atomic orbitals, we must end up with n orbital after hybridi-
zation, Figure 5.2b and eq, 5.2 show the second possibility for
the combination of a 25 and a 2p. atomic orbital. The sign
change for the combination changes the phase of the 2p.
orbital and so the resultant hybrid points in the opposite direc-
tion to the one shown in Fig. 52a, (Remember that p atomic
orbitals have vector properties.)
1
Vapyoit =e (Was ~ Yap.)
Equations 5.1 and 5.2 represent two wavefunctions which
are equivalent in every respect except for their directional-
ites with respect to the axis, Although the orbital energics
of the initial 2s and 2p, atomic orbitals were different,
mixing leads to two hybrid orbitals of equal energy.
‘The model of sp hybridization ean be used to describe
the o-bonding in a linear molecule such as BeCl, in which
the Be-Cl bonds are of equal length, The ground state
electronic configuration of Be is (Hel2s and the valence
shell contains the 2s atomic orbital and three 2p atomic
orbitals (Fig. 5.3). If we use two of these atomic orbitals,
ae
haw bovis nd
leone
Hoe
spyridization
——
Fig.
‘Scheme to show the formation of the sp hybridized valence state of a berylium atom from its ground state. This isa formalism and
is not a ‘teal’ observation, eg the valence slate cannot be observed by spectroscopic techniques, The choice of using the 2p, orbital for
hybridization is arbiay. ‘Valence bond theory: hybridization of atomic or
9+ --©@+ + —2-
e
s
a 2,
Fig. 5.4 The formation of three sp? hybrid orbitals from one 2s atomic orbital and two 2p atomic orbitals. Th
(Af we started wits 2p, and 2p, atomic orbitals, the hybrids would lic in the x= plane; using the 2p,
Pid
2», oP ybeid
oP yd
2»,
ce of p, and pis arbitrary,
and 2p, atomic orbitals gives hybrid orbitals
in the 92 plane.) The directionalities ofthe hybrid orbitals follow from the relative contbutions ofthe atomic orbitals (se egs. 52-5.)
‘eating them separately, to form two localized Be~Cl bonds,
‘we cannot rationalize the bond equivalence. However, if we
take the 2s atomic orbital and one 2p atomic orbital, mix their
characters to form sp hybrids, and use one hybrid orbital to
form one Be—Cl interaction and the other hybrid orbital for
the second interaction, then the equivalence of the Be—Cl
interactions is a natural consequence of the bonding picture.
Effectively, we are representing the valence state of Be in a
linear molecule as consisting of two degenerate sp hybrids,
‘each containing one electron; this is represented by the nota
tion (sp)’. Figure 5.3 represents the change from the ground
slate electronic configuration of Be to an sp valence
slate. This is a theoretical state which can be used to describe
bonding in a linear molecule
sp” Hybridization: a scheme for trigonal
planar species
‘The notation sp means that one s and two p atomic orbitals mix
to form a set of three hybrid orbitals with diferent directional
properties.
Let us consider the combination of 2s, 2p, and 2p, atomic
orbitals. The final hybrid orbitals must be equivalent in
every way except for their directional properties; sp”
hybrids must contain the same amount of § character as
each other and the same amount of p character as one
another. We begin by giving one-third of the 2s character
to each sp” hybrid orbital, The remaining ewo-thieds of
each hybrid orbital consists of 2p character, and the normal-
ized wavefunctions are given in eqs. 5.3 to 5.5
Vopytas 63)
Vpn (54)
Yorgns =
Figure 5.4 gives a pictorial representation of the way in
which the three sp” hybrid orbitals are constructed. Remem-
ber that a change in sign for the atomic wavefunction means
‘change in phase. The resultant directions of the lower two
hybrid orbitals in Fig. 5.4 are determined by resolving the
vectors assorated with the 2p, and 2p, atomic orbitals
"The model of sp? hybridization can be used to deseribe
the a-bonding in trigonal planar molecules such as BH.
‘The valence state of the B atom is (sp")° (ie. three sp”
hybrid orbitals, each with one electron) and the equivalence
of the B-H interactions follows by considering that each
interaction is formed by the overlap of one B sp” hybrid
orbital with the Is atomic orbital of an H atom (Fig. 5.5).
Each H_ atom contributes one electron to the bonding
scheme and, so, each B—H ¢-bond is a localized 2e-2¢ inter-
action (see Section 2.2). A diagram similar to that shown in,
Fig. 5.3 can be constructed to show the formation of a
valence state forthe trigonal planar B atom. 142. CHAPTER 5 © Bonding in polyatomic molecules
11s omic orbital
Bop yd oil
Fig. 5.5 The bonding in tigonal planar BH, can be conveniently
‘described in terms of the interactions between set of sp? hybrid
{eentred on the B atom and tree H 1s atomic orbitals. These
rs of electrons are avaiable (three electrons from B and one from
cach ID to give three 2e-2e 2-bonds.
sp° Hybridization: a scheme for tetrahedral
and related species
"The notation sp* means that one sand three p atomic orbitals
tix to form a set of four hybrid orbitals with different
siretional properties.
‘A similar scheme to those described above can be derived to
‘generate four sp* hybrid orbitals from one 2s and three 2p
‘atomic orbitals. The sp’ hybrid orbitals are described by the
normalized wavefunctions in eqs. 5.6-5.9 and are shown
pictorially in Fig. 5.6a. Each sp’ hybrid orbital possesses
25% 5 character and 75% p character, and the set of four
‘equivalent orbitals defines a tetrahedral framework.
ap? nytnia = 3 (2s + Yap, + Vay, + Uap.) (5.6)
Yap nyora = F(a + Yap, ~ Uap, ~ Yop.) (57)
Vptigiad = ban — Yap, + Vax, — van) 8)
Yap nena = (25 — Yap, ~ Yay, + Uap.) (59)
Figure 5.6b illustrates how the tetrahedral structure of CH,
relates to a cubic framework. This relationship is important
because it allows you to describe a tetrahedron in terms of a
Cartesian axis set, Within valence bond theory, the bonding
in CH, can conveniently be described in terms of an sp"
valence state for C, ie. four degenerate orbitals, each con-
taining one electron. Each hybrid orbital overlaps with the
1s atomic orbital of one H atom to generate one of four
equivalent, localized 2c-250 CH o-interactions.
e- “a
Use the VSEPR model to account for the structure of
Hy, and suggest an appropriate hybridization scheme
for the N atom.
co)
Fig. 56 (4) The dietions ofthe oil tht makeup a set
cof four phy bts correspond oa tao!
(© The relationship between a tevaedon and eben CH, the
four H toms oocupyaltemate cores ofa eae, andthe cube is
casly elated to # Canesian axis sc
The ground state electronic configuration of N is
[He]2s72p*,
Three ofthe five valence electrons are used to form three
N-H single bonds, leaving one lone pai.
‘The structure is trigonal pyramidal, derived from a
tetrahedral arrangement of electron pairs
Pac
aw
‘The N atom has four valence atomic orbitals: 2s, 2p,, 2p)
and 2p,. An sp" hybridization scheme gives a tetrahedral
arrangement of hybrid orbitals, appropriate for accom-
‘modating the four pairs of electrons:
4 Lane pa oeeiet
this hybrid nbd
N—Herbond
fermion
1. Use the VSEPR model to account for the tetrahedral
structure of [NH]
Se Axial Asal
Baal
5.7 A schematic presentation of sp'd hybridization. (8) A com
hybrid orbitals corresponding toa trigonal bipyramidal arangement; the axial spd hybrid orbitals ae directed along the
Basal
‘Valence bond theory: hybridization of atomic or
ass
Hgvatorial
quatoral autora
@
Basal
Basal
»
bination ofS, Pe Bs Ps and ds atomic orbitals gives a st of five sp'd
axis. (0) A
‘combination of, PnP. and ds,» atomic orbitals gives a set of five spd hybrid orbitals corresponding toa square-based pyramidal
futangement: the al p'dbybrid obi is dneted along the = ax
2. Rationalize why HO is bent but XeF is linear: Explain
why an sp? hybridization scheme ean be applied to HO,
‘but not to XeF
Give a suitable hybridization scheme forthe central atom
in each ofthe following: (a) [NH,]*: (b) HS; (€) BBr5s
(@) NF; (©) [HO]
{Ans (2) sp°s (0) sp?
(©) sps @) sp*s (©) sp°]
Other hybridization schemes
For molecular species with other than linear, trigonal planar
or tetrahedral-based structures, it is usual to involve d
orbitals within valence bond theory. We shall sce later
that this is not necessarily the case within molecular orbital
theory. We shall also see in Chapters 15 and 16 that the
bonding in so-called hypervalent compounds such as PFs
and SF, can be described without invoking the use of
d-orbitals. One should therefore be cautious about using
sp'd” hybridization schemes in compounds of p-block
elements with apparently expanded octets around the central
atom. Real molecules do not have to conform to simple
theories of valence, nor must they conform to the spd”
schemes that we consider in this book. Nevertheless, it is,
convenient to visualize the bonding in molecules in terms
‘of a range of simple hybridization schemes.
‘The mixing of 8, py. Py. pz and d.> atomic orbitals gives
1 set of five sp'd hybrid orbitals, the mutual orientations,
‘of which correspond to a trigonal bipyramidal arrange-
ment (Fig. 5.7a). The five sp'd hybrid orbitals are nor
equivalent and divide into sets of two axial and
three equatorial orbitals; the axial orbital lobes lic along
the z axis.) The model of sp'd hybridization can be used
to describe the o-bonding in S-coordinate species such as
[Ni(CN)5]* (see Section 21.10).
“The o-bonding framework in a square-pyramidal species
may also be described in terms of an sp'd hybridization
scheme. The change in spatial disposition of the five
hybrid orbitals from trigonal bipyramidal to square-based
pyramidal is a consequence ofthe participation of a different
4 orbital. Hybridization of s, py, p,. and d.s_,s atomic
orbitals generates a set of five sp'd hybrid orbitals
Gig. 5.70)
Hybridization of spe Py. Pos da and daz atomic orbi-
tals gives six sp'd® hybrid orbitals corresponding to an
octahedral arrangement, The bonding in MoFs can be
described in terms of sp'd? hybridization of the central
atom. If we remove the 2-components from this set (ie. p;
and da) and hybridize only the s, Py, Py and dey
atomic orbitals, the resultant set of four sp'd hybrid orbitals
corresponds to a square planar arrangement, e.g. [PtCli]”
Each sot of hybrid orbitals is associated with a particular
shape, although this may not coincide with the molecular
shape if Ione pairs also have to be accommodated
<7, linear
oor trigonal planar
oy tetrahedral
© sp'd(ds) trigonal bipyramidal
# sp'd (de) square-based pyramidal
ope octahedral
© spd square planar
‘Choice of coincidence between the 2 axis and the axial lobes is
convenient and tends fo be conventional 144 CHAPTER 5 © Bonding in polyatomic molecules
Ae storie onal
U
I)
(CC 2-50 formation
sp? hybridized C toms
®
Fig. 5.8 (a) Ethene is a planar molecule with H~C-H and C-C—H bond angles close to 120°
1 2p atomic orbital on each C atom: overlap between them gives &
appropiate ta describe the a-bonding framework. (6) This
5.3 Valence bond theory: multiple bonding
in polyatomic molecules
Inthe previous section, we emphasized that hybridization of
some orall ofthe valence atomic orbitals ofthe central atorn
in an XY, species provided a scheme for describing the
X-Y o-bonding. In, for example, the formation of sp, sp?
and sp'd hybrid orbitals, some p or d atomic orbitals
remain unhybridized and, if appropriate, may participate
in the formation of x-bonds. In this section we use the exam-
ples of C)He, HCN and BF; to illustrate how multiple bonds
in polyatomic molecules are treated within VB theory
Bofors considering the bonding in any molecule, the
‘ground state electronic configurations ofthe atoms involved
should be noted,
He
[He )2s°2p?
Hos!
Ethene, CyHg, i planar molecule (Fig, 5.88) with C-C—H
and H—C-H bond angles of 121.3° and 117.4” respectively
‘Thus, each C centre is approximately trigonal planar and the
ce-bonding. framework within CoH, can be described in
terms of an sp* hybridization scheme (Fig. 5.8b), The three
HLLe atomic orbital sp hybridized C
eo
(€-11 eon formation
@ ©
o ©
(©) An sp? hybridization scheme is
c-interactions per C atom use three of the four valence elee-
trons, leaving one electron occupying the unhybridized 2p
atomic orbital. The interaction between the two 2p atomic
onbitals (Fig. 5.8) and the pairing of the two electrons in
these atomic orbitals generates a C—C z-interation, The
bond order ofthe C—C bond in C,H, i therefore 2, in keeping
with Lewis structure 5.1. The t-component of the overall
carbon-carbon bond is weaker than the o-component
and hence a C=C double bond, though stronger than a
CC single bond, is not twice as strong. The C-C bond
enthalpy terms in CH, and C,H are 598 and 346K) mol"
respectively
4 H
\_/
ee
/ oN
H i
6.1)
HEN
© [Hep2s?2p?
N_ (He)2s*2p?
His!
Figure 5.9a shows the linear HCN molecule, a Lewis strue-
ture (5.2) for which indicates the presence of an HC single
sp hybridized
g
‘woo .
Po’
CAN etond formation
ao
J
CN bond formation CN x-bond formation
©
Fig. 5.9 (a) The linear structure of HCN; colour code: C, grey; N, blue; H, white. (b) An sp hybridization scheme for C and N can be
used to describe the o-bonding in HCN. (€) The character in the C-N bond arses from 2p 2p overlap. Valence bond theory: multiple bonding in polyatomic molecules
(5.2)
bond, a C=N triple bond, and a lone pair of electrons on N.
‘An sp hybridization scheme is appropriate for both C and Ns,
it is consistent with the linear arrangement of atoms around
‘Cand with the placement of the lone pair on N as far away
‘as possible from the bonding electrons. Figure 5.9 shows
the o-bonding framework in HCN (each region of orbital
overlap is occupied by a pair of electrons) and the out-
FE _f :
\
>
Fully ocewpied 2p
some orbital on F
Fig. 5.10 (a) BF, possesses a tigonal planar structure, (©) 2p-2p
‘overlap between B and F leads to the formation ofa interaction,
(6) Boros-fivorine double bond characteris also deduced by
considering the resonance structures for BF; only those forms that,
contsibute significantly are shown
145
‘ward-pointing sp hybrid on N that accommodates the lone
pair. If we arbitrarily define the HCN axis as the 2 axis,
then afler the formation of the @-interactions, a 2p, and a
2p, atomic orbital remain on each of the C and N atoms.
Each atomic orbital contains one electron. Overlap between,
the two 2p, and between the two 2p, orbitals leads to two
sr-interactions (Fig. 5.9). The overall C-N bond order
is 3, consistent with Lewis structure 5.2.
BF;
B (He)2s*2p!
F (He)2s*2p*
Boron trifluoride (Fig. 5.10a) is trigonal planar (D3,), and
sp? hybridization is appropriate for the B atom, Each of
the three B-F o-interactions arises by overlap of an sp?
hybrid on the B atom with, for example, an sp” orbital on
the F atom. After the formation of the o-bonding framework,
the B atom is let with an unoccupied 2p atomic orbital lying
perpendicular to the plane containing the BF molecule. As
Fig. 5.10 shows, this is ideally set up for interaction with a
{filled 2p atomic orbital on one of the F atoms to give a loca-
lized B—F r-interaction. Notice thatthe two electrons occu-
pying this x-bonding orbital both originate from the F atom.
This picture ofthe bonding in BF; is analogous to one of the
resonance forms shown in pink in Fig. 5.10c. All three reso-
hance forms (see Section 2,2) are needed to account for the
experimental observation that the three B—F bonds are of
equal length (131 pm).
eS —
(a) The [NOs}” ion has Dy, symmetry. What does this
tell you about its structure? (b) Draw a set of resonance
structures (focusing only on those that contribute
significantly) for the nitrate ion. (c) Use an appropriate
yb m scheme to describe the bonding in [NOs] .
(#) If[NOs}” has Day symmetry it must be planar, possess
O-N-O bond angles of 120°, and have equal N-O bond
distances,
(b) First, write down the electronic configurations for N
(Z=7) and O (Z = 8).
N Heep? °
[easton
‘There is an additional electron from the negative charge
giving a total of 24 valence electrons.
Both N and O obey the octet rule and so the most impor-
tant resonance forms are expected to be: 146 CHAPTER 5 © Bonding in polyatomic molecules
(©) Using a hybridization scheme, we should end up with
bonding picture that corresponds to that depicted by the
resonance structures,
An sp? hybridized nitrogen centre is consistent with the
trigonal planar shape of [NO,]-. Allow the hybrid orbitals
to overlap with suitable orbitals from oxygen. A choice of
sp" hybridization on the O atom provides suitable orbitals
to accommodate the oxygen lone pairs. Occupation of
each bonding orbital by a pair of electrons gives three
equivalent N—O o-bonds:
NO cbonding interaction
=p yin a on ort,
ected le pi of decons
Of the 24 valence electrons, 18 are accommodated cither in
a-bonds or as oxygen lone pairs
“The next step isto consider multiple bonding character
Each N and O atom has an unused 2p atomic orbital ying
perpendicular tothe plane ofthe molecule. Six valence elec-
trons are available. Overlap between the 2p atomic orbital
‘on nitrogen with one of those on an oxygen atom gives
rise to one localized 1-bond. The six valence electrons are
allocated as follows with the N centre treated as N
ineseh of two oxygen
2patomic omitale
(ne pair of letone for NO x-bond formation
‘Thecombination ofthe ¢- and r-bonding pictures gives one
nitrogen-oxygen double bond and two single bonds, Three
such schemes must be drawn (with the 7-character in one of
each of the NO bonds) in order that the overall scheme is
in keeping with the observed Dy, symmetry of [NOs]
1, Why are resonance structures containing two N=O double
bonds not included in the sct shown above for [NOs]?
2. Use an appropriate hybridization scheme to deseribe the
bonding in (BO,]°
5.4 Molecular orbital theory: the ligand
group orbital approach and application
to triatomic molecules
Despite its successes, the application of valence bond theory
to the bonding in polyatomic molecules leads to conceptual
difficulties. The method dictates that bonds are localized
land, as a consequence, sets of resonance structures and
bonding pictures involving hybridization schemes become
rather tedious to establish, even for relatively small
‘molecules (c.g. see Fig. 5.10c). We therefore tum our atten-
tion to molecular orbital (MO) theory.
Molecular orbital diagrams: moving from a
diatomic to polyatomic species
|AS part of our treatment of the bonding in diatomics in
Section 2.3, we constructed MO diagrams such as
Figs. 2.8, 2.14 and 2.15. In each diagram, the atomic orbitals,
of the two atoms were represented on the right- and left.
hhand sides of the diagram with the MOs in the middle.
Correlation lines connecting the atomic and molecular orbi-
tals were constructed to produce a readily interpretable
diagram,
Now consider the situation for a triatomic molecule
such as CO3. The molecular orbitals contain contributions
from the atomic orbitals of three atoms, and we are pre-
sented with a problem of trying to draw an MO diagram
involving four sets of orbitals (three sets of atomic orbitals
and one of molecular orbitals). A description of the bond-
ing in CF, involves five sets of atomic orbitals and one set
of molecular orbitals, ic. a six-component problem. Simi-
larly, SF is an eight-component problem. It is obvious
that such MO diagrams are complicated and, probably,
difficult both to construct and to interpret. In order to over-
come this difficulty, it is common to resolve the MO
description of a polyatomic molecule into a three-compo-
nent problem, a method known as the ligand group orbital
(LGO) approach.
MO approach to bonding in linear XH.
matching by inspection
Initially, we illustrate the ligand group orbital approach
by considering the bonding in a linear tristomic XH in,
which the valence orbitals of X are the 2s and 2p atomic
orbitals. Let us orient the H—X—H framework so that it
coincides with the 7 axis as shown in Fig. 5.11. Consider
the two Is atomic orbitals of the two H atoms, Each 1s
atomic orbital has two possible phases and, when the 10
1s orbitals are taken as a group, there are two possible
phase combinations. These are called ligand group orbitals Molecular orbital theory: the ligand group orbital approach and application to triatomic molecules. 147
Fig. 5.11 Application ofthe ligand group orbital (LGO) approach to construct a qualitative MO di
le fom the interactions of the valence orbitals of X Cs and 2p atomie orbitals) and an H-
sl
1600)
DD errst phase
@ oe
(acpase)
x,
sam for the formation of a linear XH:
Tragment, For clarity, the lines marking
the 2p orbital energies are drawn span, although these atomic orbitals ar degenerate.
e@o @eD
% % %
X—Hbonding character
Centeed on stom X
@ ole 66
2 O09 o@
%, %
X—H antibonding character
5.12 The lower diagrams are schematic representations ofthe MOs in linear XHp, The wavefunction labels correspond to thse in
Fig. 5.11. The upper diagrams are more realistic representations af the MOs and have been generated computationally using Spartan "04
©) Wavefunction Ine, 2003,
(LG0s) and are shown at the right-hand side of Fig. 5.11.7
Effectively, we are transforming the description of the
bonding in XH; from one in which the basis sets are the
atomic orbitals of atoms X and H, into one in which
the basis sets are the atomic orbitals of atom X and the
ligand group orbitals of an H---H fragment. This is a
valuable approach for polyatomic molecules.
‘The number of ligand group orbitals formed = the number of
atomic orbitals used.
“in Fig. 5.11, the energies of the two ligand group orbitals ae close
together Because the Hl nuclei are far apart; compare this with the
situation in the Hp molecule (Fig. 25). Similarly, in Fig. 5.17, the
LGOs for the Hs fragment form two sets (all in-phase, and the degen:
crit prof orbitals) bu their rexpoctive energies are close because of
the large H---H separations,
In constructing an MO diagram for XH (Fig. 5.11), we
consider the interactions of the valence atomic orbitals of
X with the ligand group orbitals of the H---H fragment.
Ligand group orbital LGO(1) has the correct symmetry to
interact with the 2s atomic orbital of X, giving an MO
with H—X—H o-bonding character. The symmetry of
L.GO(2) is matched to that of the 2p. atomic orbital of X.
‘The resultant bonding MOs (v; and vz) and their antibond-
ing counterparts (y's and vs) are shown in Fig, 5.12, and the
MO diagram in Fig. 5.11 shows the corresponding orbital
interactions, The 2p, and 2p, atomic orbitals of X become
‘non-bonding orbitals in XH, The final step in the construc
tion of the MO diagram is to place the available electrons in
the MOs according to the aufbau principle (see Section 1.9).
‘An important result of the MO treatment of the bonding in, 148 CHAPTER 5 © Bonding in polyatomic molecules
XH, is that the o-bonding character in orbitals yy and
‘Yn is spread over all three atoms, indicating that the
bonding character is delocalized over the H—X—H frame-
work, Delocalized bonding is a general result within MO.
theory.
MO approach to bonding in linear XH:
working from molecular symmetry
‘The method shown above for generating a bonding descrip-
tion for linear XH cannot easily be extended to larger
‘molecules, A more rigorous method is to start by identifying
the point group of linear XH a8 Dag, (Fig. 5.13a). The Daoy,
character table is used to assign symmetries to the orbitals,
‘on atom X, and to the ligand group orbitals. The MO dia
‘gram is then constructed by allowing interactions between,
orbitals of the same symmetry. Only ligand group orbitals
that can be classified within the point group of the whole
‘molecule are allowed.
Unfortunately, although a linear XH; molecule is structa-
rally simple, the D,.y, character table is not. This, therefore,
‘makes a poor first example of the use of group theory in
orbital analysis. We can, however, draw an analogy betwes
the symmetries of orbitals in linear XH; and those in homo-
nuclear diatomics (also Dau,). Figure 5.13b is a repeat of
Fig. 5.11, but this time the symmetries of the orbitals on
atom X and the two ligand group orbitals are given, Com
pare these symmetry labels with those in Figs. 2.6 and 2.7,
‘The construction of the MO diagram in Fig. 5.13b follows
by allowing interactions (bonding or antibonding) between
cobitals on atom X and ligand group orbitals with the
same symmetry labels
i
5 Gninite mmber)
a
ai
©.
©
A bent triatomic: H20
‘The H;0 molecule has C2, symmetry (Fig. 5.14) and we
now show how to use this information to develop an MO
picture of the bonding in HO. Part of the C3, character
table is shown below:
G
1
I
l
1
1
1
1
1
‘The inclusion of the xz and p2 terms in the last two columns
of the character table spevfies that the HO molecule is
taken to lie in the y2 plane, ie. the 2 axis coincides with
the principal axis (Fig, 5.14), The character table has several
important features.
‘© The labels in the fist column (under the point group
symbol) tell us the symmetry types of orbitals that are
permitted within the specified point group.
‘© The numbers in the column headed £ (the identity
‘operator indicate the degeneracy of each type of orbitals
inthe Co, point group, all orbitals have a degeneracy of I,
ive. they are non-degenerate
zach row of numbers following a given symmetry label
indicates how a particular orbital behaves when operated
upon by each symmetry operation. A number 1 means
that the orbital is unchanged by the operation, a —1
‘means the orbital changes sign, and a 0 means that the
orbital changes in some other way.
ayiny @ Gros,
21) 5
neo \/ @ Qr000 4,
Be
x xt, "
n—x—a—,
®
Fig. 5.13 (a) A linear XI, molecule belongs to the D. point group. Some of the symmetry elements are shown; the X atom lies on a
conte of symmecy (inversion centre). (0) A qualitative MO diagram for she formation of linear XH. from stom X and two H atoms Molecular orbital theory: the ligand group orbital approach and application to triatomic molecules 149
ely ete wits)
|
a0)
02)
Fig. 5.14 The H1,0 molecule possesses « C, axis and two oy
planes and belongs tothe Co, point group
To illustrate its use, let us consider the 2s atomic orbital of
the O atom i water:
2 atomic omit of oxygen
Apply cach symmetry operation of the C>y point group in
tum. Applying the £ operator Ieaves the 2s atomic orbital
‘unchanged. Rotation about the C3 axis leaves the atomic
orbital unchanged. Reflections through the and 0,"
planes leave the 25 atomic orbital unchanged. These results,
correspond to the following row of characters:
oN
« "
G ale a0)
1 1 1 1
and this matches those forthe symmetry type j in the Ca
character table, We therefore label the 2s atomic orbital on
the oxygen atom in water as an a orbital (Lowercase letters
are used forthe orbital label, but upper case forthe symmetry
type in the character table.) The same testis now cartied out
‘on each atomic orbital of the O atom. The oxygen 2p, orbital
is left unchanged by the E operator and by reflection through
the o,(x2) plane. Each of rotation about the C; axis and
reflection through the o,'(y2) plane inverts the phase of the
2p, orbital. This is summarized as follows:
E G
antes) a0)
1 -l 1
‘This matches the row of characters for symmetry type By in
the Cyy character table, and the 2p, orbital therefore pos-
sesses by symmetry. The 2p, orbital is left unchanged by
the F operator and by reflection through the 2y'(»2) plane,
but rotation about the C axis and reflection through the
‘ov(x2) plane each inverts the phase of the orbital, This is,
summarized by the row of characters:
‘This corresponds to symmetry type By in the Cyy character
table, and the 2p, orbital is labelled by. ‘The 2p. orbital is
Teft unchanged by the F operator, by reflection through
either of the oy(x2) and ,'(%2) planes, and by rotation
about the Cy axis. Like the 2s orbital, the 2p. orbital
therefore has ay symmetry.
The next step is 0 work out the nature of the H-—-H
ligand group orbitals that are allowed within the Cay point
aroup. Since we start with two H Is orbitals, only vo
L.GOs can be constructed. The symmetries of these LGOs
are deduced as follows. By looking at Fig. 5.14, you can
see what happens to cach of the two H 1s orbitals when
cach symmetry operation is performed: both 1s orbitals
are left unchanged by the E operator and by reflection
through the ,'(92) plane, but both are affected by rotation
about the C) axis and by reflection through the (x2)
plane. This information is summarized in the following
row of characters
E G entx2)
ava)
2 0 0 2
in which a2" shows that two orbitals are unchanged by the
operation’, and a°0° means that ‘no orbitals are unchanged
by the operation’. Next, we note two facts: () we ean con-
struct only vo ligand group orbitals, and (i) the symmetry
of each LGO must correspond to one ofthe symmetry types
in the character table. We now compare the row of charac-
ters above with the swms of two rows of characters in the
C2, character table, A match is found with the sum of the
characters for the y and By representations, AS a result,
we ean deduce thatthe two LGOs must possess ay and by
symmetries, respectively. In this case, it is relatively
straightforward to use the a; and by symmetry labels to
sketch the LGOs shown in Fig. 5.15, ie. the 4 orbital
corresponds to an in-phase combination of H.1s orbitals,
‘while the by orbital is the out-of-phase combination of H
1s otbitals. However, once their symmetries are known,
the rigorous method of determining the nature of the orbitals
is as follows
Let the Is orbitals ofthe two H atoms shown in Fig. 5.14
be designated as vy and ya. We now look atthe effect of
cach symmetry operation of the C3, point group on vi
‘The E operator and reflection through the 9,
plane (Fig, 5.14) leave vy unchanged, but a Cy
fotation and reflection through the oy(xz) plane each 150
CHAPTER 5 © Bonding in polyatomic molecules
Energy
Representation of the 5, MO
&
Repreeotation ofthe higher energy 2, MO
Representation of heb, MO
Representation ofthe lower energy 9) MO
Fig. 5.15 A qualitative MO diagram forthe formation of H30 using the ligand group orbital approach. The two H atonss in the Hp fragment are
‘out of bonding range with each other, thir positions being analogous to those in HO. For clarity, the lines marking the oxygen 2p orbital
‘energies are drawn apart, despite ther being degenerate. Representations of the occupied MOS are shown athe right-hand side ofthe figure
Wat
(generated with Spartan ‘04,
function Inc. 2003). For the a, and fy MOs the HO molecule isi te plane ofthe paper, forthe by MO,
the plane containing the molecule is perpendicular to the plane ofthe paper,
transforms vy into Wa. The results are written down as a row
of characters:
To determine the composition of the a LGO of the
H---H fragment in H,O, we multiply cach character in
the above row by the corresponding character for the A,
representation in the Czy character table, is
cy |e G (x2) @/'02)
A 1 1 1 1
‘The result of the multiplication is shown in eq. 5.10 and
‘gives the unnormalized wavefunction for the a; orbital
(ay) = (1 va) + (1 oa) + (Leva) + (ew)
= Wy +2 (5.10)
‘This can be simplified by dividing by 2 and, after normal
zation (see Section 2.2), gives the final equation for the
‘wavefunction (eg, 5.11).
va) = (v1 + v2)
inphase combination
v2 ”
(sl)
Similarly, by using the B, representation in the Cz, charac
ter table, we can write down eq. 5.12. Equation 5.13 gives,
the equation for the normalized wavefunction.
(Pa) = (Lx va) = (1 x va) = (1x aa) + (Le a)
= 20, - 2a (5.12)
1
(bs) = Fe (Ui — ¥2) out-of-phase combination (5.13)
(ba) = Fala ~ va) outofen
‘The MO diagram shown in Fig. 5.15 is constructed as fol-
ows. Bach of the 2s and 2p. orbitals of the O atom possesses
the correct symmetry (a;) o interact with the a; orbital ofthe
H--H fragment. These orbital interactions must lead 10.
three MOs: two bonding MOs with a; symmetry and one
antibonding (a,") MO. On symmetry grounds, the lower
energy a, MO could also include 2p, character, but 2s
character dominates because of the energy separation of
the 2s and 2p, atomic orbitals. The interaction between the Molecular orbital theory applied to the polyatomic molecules BH, NH and CH, 151
2p, atomic orbital and the LGO with by symmetry leads to
‘two MOs which possess H-O—H bonding and antibonding
character respectively. The oxygen 2p, orbital has b, sym-
‘metry and there is no symmetry match with a ligand group
‘orbital, Thus, the oxygen 2p, orbital is non-bonding in HO.
‘The eight valence electrons in Hj occupy the MOs
according to the aufbaw principle, and this gives rise to
two occupied H-O-H bonding MOs and two occupied
Os with mainly oxygen character. (To appreciate this
fully, see end-of-chapter problem 5.12.) Although this bond-
ing model for HO is approximate, it is qualitatively
adequate for most descriptive purposes
5.5 Molecular orbital theory applied to
the polyatomic molecules BHs, NH3
and CH,
‘We begin this section by considering the bonding in BH,
and NH. The bonding in both molecules involves ¢-inter-
actions, but whereas BH has Dy, symmetry, NH, belongs
to the Cyy point group.
BHs
‘The existence of BH, in the gas phase has been established
even though the molecule readily dimerizes; the bonding in
[BH is described in Section 5.7. The BH molecule belongs
to the Dy, point group. By considering the orbital inter-
actions between the atomic orbitals of the B atom and the
LGOs of an appropriate Hy fragment, we can establish a
molecular bonding scheme, We begin by choosing an
appropriate axis set. The z axis coincides with the Cy axis
of BH, and all of the atoms lie in the xy plane. Part of the
Ds character table is shown in Table 5.1. By using the
same approach as we did for the orbitals of the O atom in
HO, we can assign symmetry labels to the orbitals of the
B atom in BH:
4 the 2s ombital has a symmetry:
© the 2p, orbital has a," symmetry;
«the 2p, and 2p, orbitals are degenerate and the orbital set
has e symmetry.
Table 5.1. Partofthe Dy character able; the complete table is given
in Appendix 3
Dy E 2% % Boy
Ay toot 1 1 1 1
ay boob at 1 el
E 20-1 2-1 0
4 14 PoP ta
4; ee
2-1 0 2 an)
1 86 MBH mote a Dy ym
We now consider the nature of the three ligand group
orbitals that are formed from linear combinations of the
three H Is orbitals. By referring to the Hy-fragment in
BH, we work out how many H 1s orbitals are left
unchanged by each symmetry operation in the D3, point
group (Fig. 5.16). The result is represented by the following.
row of characters:
GQ %% Ss
3 0 1 3 0 1
‘This same row of characters canbe obtained by summing
the rows of characters forthe 4," and E* representations in
the Dg, character table, Thus, the three LGOs have a and
@ symmeties; recall tat the ¢ label designates a doubly
degenerate st of orbitals. We must now determine the wave-
function for each LGO. Let the tree H 1s orbitals inthe Hy
fragment in BH, be vy, va and Ws. The next sep is 0 see
how vis affected by cach symmetry operation of the Dag
point group (Fig. 5.16), For example, the C; operation trans-
forms into ds the C} operation transforms ¥ into Yi, and
the tee Cy operations, respectively, lave ¥, unchanged,
transform into Yad transform into o, The follow-
ing row of characters gives the complete result:
EG G a) 42 4) a»
a ee ee ee
So) 42) 0)
Bok
‘The unnormalized wavefunction (eq. 5.14) for the ay"
ligand group orbital is found by multiplying each
character in the above row by the corresponding character
for the Ay" representation in the Dy, character table. After 152 CHAPTER 5 © Bonding in polyatomic molecules
Energy
2»,
27,27,
2a)
G
Represeataton ofthe LUMO (e,")
Repretentation of the degenerate HOMO (¢)
Representation ofthe lowest ing MO
Fig. 5.17 A qualitative MO diagram forthe formation of BH, using the ligand group orbital approach. The three H atoms in the Hy
Fragment are out of bonding range with each other, their positions being analogous to those in the BH molecule. Oxbitals LGOQ2) and
156043) form a degenerate pair ( symmety) although, for clarity, the lines marking their orbital energies ate drawn apart; simile forthe
three 2p atomic orbitals of boron. (Exercise: where do the nodal planes le in LGOX2) and LGO(3)?} The diagrams a the right-hand side show
representations ofthe thre occupied MOs and the LUMO (generated with Spartan ‘04, (©Wavefunction Inc. 2003).
simplification (dividing by 4) and normalizing, the wave-
function can be written as eq, 5.15, and can be described
schematically as the in-phase combination of Ls orbitals
shown as LGO() in Fig. 5.17.
Ua) = Yat Unt a ta Ht a
4M the
= 4 + Aa + 4s (5.14)
1
lar) = a(n + oe + vs) (5.15)
I= 5)
‘A similar procedure can be used to deduce that eq. 5.16
describes the normalized wavefunction for one of the degen:
erate e' orbitals. Schematically, this is represented as
LGOQ2) in Fig. 5.17; the orbital contains one nodal plane.
ie), — Lv) — a —
Me) = FOV — v=o) (5.16)
Each é orbital must contain a nodal plane, and the planes in,
the two orbitals are orthogonal to one another. Thus, we can
write eq. 5.17 to describe the second e' orbital; the nodal
plane passes through atom H(1) and the Ls orbital on this
‘atom makes no contribution to the LGO. This is,
represented as LGO(3) in Fig. 5.17,
Vien = (Wa — va) (5.17)
vi
‘The MO diagram for BH ean now be constructed by allow
ing orbitals of the same symmetry (0 interact. The 2p.
orbital on the B atom has a)" symmetry and no symmetry
match can be found with an LGO of the Hy fragment
Thus, the 2p, orbital is non-bonding in BH,. The MO
approach describes the bonding in BH) in terms of three
MOs of ay’ and e° symmetries. The a," orbital possesses
‘-bonding character which is delocalized over all four
atoms. The e' orbitals also exhibit delocalized character,
and the bonding in BH, is described by considering a com-
bination of all three bonding MOs
NHs
‘The NH molecule has C3, symmetry (Fig. 5.18) and a
bonding scheme can be derived by considering the inter-
action between the atomic orbitals of the N atom and the
ligand group orbitals of an appropriate Hy fragment. An Molecular orbital theory applied to the polyatomic molecules BH, NH, and CH, 153
Table 5.2 Part ofthe Cy. character table; the complete table is given
ass
in Appendix 3
Cw E 20, Boy
A 1 t 1
As 1 I a
E 2 -1 o
To determine the nature of the ligand group orbitals, we con-
sider how many H 1s orbitals are left unchanged by each
symmetry operation in the Cy point group (Fig. 5.18).
The result is represented by the row of characters:
BPH DEN ste he Gyms
E Gow
appropriate axis sot has the axis coincident with the C3 >— TT
axis of NIL; (Sce worked example 3.2); the x andy axes
are directed as shown in Fig, 5.19, Table 5.2 shows part of
the Cy, character table, BY seeing how cach symmetry follows that the three igand group orbitals have a and
operation affects each orbital of the N atom in NHy, the © S¥mmetries. Although the symmetry labels of the LGOs
orbital symmetries are assigned as follows of the Hy fragments in NH; and BHs differ because the
‘molecules belong to different point groups, the normalized
+ cach of the 2s and 2p, orbitals has ay symmetry: ‘wavefunctions for the LGOs are the same (eqs. 5.15-5.17)
‘© the 2p, and 2p, orbitals are degenerate and the orbital set Schematic representations of the LGOs are shown in
has e symmetry. Fig. 5.19,
3 0 1
Boeegy
eo”
6-8 6-@
10a) L608)
a0)
wt a eprstntion ote HOMO)
104)
20)
hm epsttion fone ofthe eMOs
Repretettation ofthe lowe ing 4, MO
-
Fig. 5.19 A qualitative MO diagram for the formation of NH using the ligand group orbital approach. For clay, the lines marking
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