Covalent Bonding & Covalent Bonding &

Molecular Orbital Theory Molecular Orbital Theory

Chemistry 754 Chemistry 754
Solid State Chemistry Solid State Chemistry
Dr. Patrick Woodward Dr. Patrick Woodward
Lecture #16 Lecture #16
References - MO Theory References - MO Theory
Molecular orbital theory is covered in many places Molecular orbital theory is covered in many places
including most general inorganic chemistry texts. including most general inorganic chemistry texts.
The material for this lecture (along with many of the The material for this lecture (along with many of the
figures) was taken from the following two texts: figures) was taken from the following two texts:
Orbital Interactions in Chemistry Orbital Interactions in Chemistry
Thomas Albright, Jeremy K. Burdett & Thomas Albright, Jeremy K. Burdett & Myung Myung- -Hwan Whangbo Hwan Whangbo, ,
Wiley & Sons, New York (1985). Wiley & Sons, New York (1985).
Chemical Bonding in Solids Chemical Bonding in Solids
Jeremy K. Burdett, Oxford University Press, Oxford (1995). Jeremy K. Burdett, Oxford University Press, Oxford (1995).
Questions to Consider Questions to Consider
Why is H Why is H
2 2
O bent rather than linear? Why is NH O bent rather than linear? Why is NH
3 3
pyramidal rather than planar? pyramidal rather than planar?
Why are Why are Sn Sn and and Pb Pb metals, while metals, while Si Si and and Ge Ge are are
semiconductors? semiconductors?
Why are the Why are the electrons electrons delocalized delocalized in benzene (C in benzene (C
6 6
H H
6 6
) )
and localized in and localized in cyclobutadiene cyclobutadiene (C (C
4 4
H H
4 4
)? )?
In oxides, In oxides, chalcogenides chalcogenides and halides explain the and halides explain the
following coordination preferences: following coordination preferences:
Cu Cu
2+ 2+
& Mn & Mn
3+ 3+
distorted octahedral environment distorted octahedral environment
Ni Ni
2+ 2+
and Fe and Fe
3+ 3+
regular octahedral environment regular octahedral environment
Pd Pd
2+ 2+
and Pd and Pd
2+ 2+
square planar environment square planar environment
Pb Pb
2+ 2+
, Sn , Sn
2+ 2+
, Bi , Bi
3+ 3+
, Sb , Sb
3+ 3+
asymmetric coordination environment asymmetric coordination environment
MO Diagram for H MO Diagram for H
2 2
The number of MOs is equal to the The number of MOs is equal to the
number of atomic number of atomic orbitals orbitals. .
Each MO can hold 2 electrons (with Each MO can hold 2 electrons (with
opposite spins). opposite spins).
The The antibonding antibonding MO has a nodal plane MO has a nodal plane
between atoms and between atoms and to the bond. to the bond.
As the spatial overlap increases As the spatial overlap increases
1 1
(bonding MO) is stabilized and (bonding MO) is stabilized and
2 2
( (antibonding antibonding MO) is destabilized. MO) is destabilized.
The destabilization of the The destabilization of the antibonding antibonding
MO is always greater than the MO is always greater than the
stabilization of the bonding MO. stabilization of the bonding MO.
In the diagrams at the top and bottom the solid line
denotes the electron density from MO theory and the
dashed line the electron density from superimposing to
atomic orbitals.
E
1 1
st st
Order MO Diagram for O Order MO Diagram for O
2 2
The 2s The 2s orbitals orbitals have a lower energy have a lower energy
than the 2p than the 2p orbitals orbitals. .
The The -bonds have a greater spatial -bonds have a greater spatial
overlap than the overlap than the -bonds. This leads to -bonds. This leads to
a larger splitting of the bonding and a larger splitting of the bonding and
antibonding orbitals antibonding orbitals. .
The 2p The 2p
x x
and 2p and 2p
y y
-interaction produces -interaction produces
to two sets of degenerate to two sets of degenerate orbitals orbitals. .
The MOs have symmetry descriptors, The MOs have symmetry descriptors,

g g
+ +
, ,
u u
+ +
, ,
g g
, ,
u u
within point group D within point group D
h h
. .
Mixing is allowed between MO Mixing is allowed between MO s of the s of the
same symmetry. same symmetry.
In O In O
2 2
there are 12 valence electrons there are 12 valence electrons
and each of the 2p and each of the 2p
* *
orbitals orbitals ( (
g g
) are ) are
singly occupied. Thus the bond order = singly occupied. Thus the bond order =
2, and O 2, and O
2 2
is paramagnetic. is paramagnetic.
E
2 2
nd nd
Order MO Diagram for O Order MO Diagram for O
2 2
(N (N
2 2
) )
A more accurate depiction of the bonding A more accurate depiction of the bonding
takes into account mixing of of MOs with takes into account mixing of of MOs with
the same symmetry ( the same symmetry (
g g
+ +
& &
u u
+ +
). The ). The
consequences of this 2 consequences of this 2
nd nd
order effect are: order effect are:
The lower energy orbital is stabilized while The lower energy orbital is stabilized while
the higher energy orbital is the higher energy orbital is destablized destablized. .
The s and p character of the The s and p character of the MOs MOs
becomes mixed. becomes mixed.
The mixing becomes more pronounced as The mixing becomes more pronounced as
the energy separation decreases. the energy separation decreases.
E
The atomic The atomic orbitals orbitals of the more of the more
electronegative atom are lowered. electronegative atom are lowered.
The splitting between bonding and The splitting between bonding and
antibonding antibonding MOs now has an ionic ( MOs now has an ionic (E E
i i
) )
and a covalent ( and a covalent (E E
c c
) component. ) component.
The ionic component of the splitting ( The ionic component of the splitting (E E
i i
) )
increases as the increases as the electronegativity electronegativity
difference increases. difference increases.
The The covalency covalency and the covalent and the covalent
stabilization/destabilization decrease as stabilization/destabilization decrease as
the the electronegativity electronegativity difference difference
increases. increases.
The orbital character of the more The orbital character of the more
electronegative atom is enhanced in the electronegative atom is enhanced in the
bonding MO and diminished in the bonding MO and diminished in the
antibonding antibonding MO. MO.
Heteronuclear Heteronuclear Case & Case & Electronegativity Electronegativity
E
E
i
Linear AX Linear AX
2 2
(H (H
2 2
O) MO Diagram O) MO Diagram
In linear H In linear H
2 2
O the O 2s and O 2p O the O 2s and O 2p
z z
orbitals orbitals could form could form -bonds to H, -bonds to H,
while the O 2p while the O 2p
x x
& 2p & 2p
y y
orbitals orbitals
would be non-bonding. would be non-bonding.
Bent AX Bent AX
2 2
(H (H
2 2
O) MO Diagram O) MO Diagram
In bent H In bent H
2 2
O the O 2s O the O 2s

orbital and orbital and
the O 2p the O 2p
x x
orbital are allowed to mix orbital are allowed to mix
by symmetry, lowering the energy of by symmetry, lowering the energy of
the O 2p the O 2p
x x
orbital. Now there is only orbital. Now there is only
one non-bonding orbital (O 2p one non-bonding orbital (O 2p
y y
) )
Walsh Diagrams & 2 Walsh Diagrams & 2
nd nd
Order JT Distortions Order JT Distortions
HOMO HOMO
Walsh Diagram Walsh Diagram
Shows how the MO levels vary as a Shows how the MO levels vary as a
function of a geometrical change. function of a geometrical change.
Walshs Rule Walshs Rule
A molecule adopts the structure A molecule adopts the structure
that best stabilizes the HOMO. If that best stabilizes the HOMO. If
the HOMO is unperturbed the the HOMO is unperturbed the
occupied MO lying closest to it occupied MO lying closest to it
governs the geometrical governs the geometrical
preference. preference.
2 2
nd nd
Order Jahn-Teller Dist. Order Jahn-Teller Dist.
A molecule with a small energy gap A molecule with a small energy gap
between the occupied and between the occupied and
unoccupied MOs is susceptible to a unoccupied MOs is susceptible to a
structural distortion that allows structural distortion that allows
intermixing between them. intermixing between them.
Idealized Idealized - -Cristobalite Cristobalite (SiO (SiO
2 2
) )
Space Group = Fd3m (Cubic) Space Group = Fd3m (Cubic)
Si Si-O- -O-Si Si = 180 = 180
sp bonding at O sp bonding at O
2- 2-
, ,
2 nonbonding O 2p 2 nonbonding O 2p orbitals orbitals
Actual Actual - -Cristobalite Cristobalite (SiO (SiO
2 2
) )
Space Group = I-42d (Tetragonal) Space Group = I-42d (Tetragonal)
Si Si-O- -O-Si Si = 147 = 147
sp sp
2 2
bonding at O bonding at O
2- 2-
Covalent Bonding & the Structure of Covalent Bonding & the Structure of
Cristobalite Cristobalite
Walsh Diagram for NH Walsh Diagram for NH
3 3
HOMO HOMO
In the planar (D In the planar (D
3h 3h
) )
form the HOMO is a form the HOMO is a
non-bonding O 2p non-bonding O 2p
orbital (a orbital (a
2 2
) containing ) containing
2 electrons. 2 electrons.
In the pyramidal (C In the pyramidal (C
3v 3v
) )
form the N 2s H 1s form the N 2s H 1s
* *
orbital (a orbital (a
1 1
) can mix ) can mix
with the nonbonding O with the nonbonding O
2p orbital. Stabilizing 2p orbital. Stabilizing
the HOMO. the HOMO.
Tetrahedral AX Tetrahedral AX
4 4
(CH (CH
4 4
) MO Diagram ) MO Diagram
Notice that while both the 2s Notice that while both the 2s
and 2p and 2p orbitals orbitals on Carbon are on Carbon are
involved in bonding, in a perfect involved in bonding, in a perfect
tetrahedron mixing of the s (a tetrahedron mixing of the s (a
1 1
) )
and p (t and p (t
2 2
) ) orbitals orbitals is forbidden. is forbidden.
Diamonds and Lead Diamonds and Lead
Structure & Properties of Structure & Properties of
the Group 14 Elements the Group 14 Elements
Element Element Structure Structure E E
g g
( (eV eV) )
C C Diamond Diamond 5.5 5.5
Si Si Diamond Diamond 1.1 1.1
Ge Ge Diamond Diamond 0.7 0.7
- -Sn Sn Diamond Diamond 0.1 0.1
- -Sn Sn Tetragonal Metal Tetragonal Metal
Pb Pb FCC FCC Metal Metal
As you go proceed down the group As you go proceed down the group
the tendency for the s- the tendency for the s-orbitals orbitals
to become involved in bonding to become involved in bonding
diminishes. This destabilizes diminishes. This destabilizes
tetrahedral coordination and tetrahedral coordination and
semiconducting semiconducting/insulating /insulating
behavior. behavior.
2p 2p
2s 2s
2p 2p
2s 2s
a a
1 1
a a
1 1
* *
t t
2 2
t t
2 2
* *
C C
6p 6p
6s 6s
a a
1 1
a a
1 1
* *
t t
2 2
t t
2 2
* *
Pb Pb
6p 6p
6s 6s
2 2
nd nd
Order JT Distortion in Order JT Distortion in PbO PbO
Pb Pb 6s 6s
HOMO HOMO
In both polymorphs of In both polymorphs of PbO PbO (red (red PbO PbO, the tetragonal form is shown above) the Pb , the tetragonal form is shown above) the Pb
2+ 2+
ions adopt a very asymmetric coordination environment. The driving force for this ions adopt a very asymmetric coordination environment. The driving force for this
is to lower the energy of the filled, is to lower the energy of the filled, antibonding Pb antibonding Pb 6s 6s orbitals orbitals, by mixing with an , by mixing with an
empty empty Pb Pb 6p orbital. Such mixing is forbidden by symmetry in tetrahedral and 6p orbital. Such mixing is forbidden by symmetry in tetrahedral and
octahedral coordination, so a distortion to a lower symmetry leading to the octahedral coordination, so a distortion to a lower symmetry leading to the
formation of the so-called formation of the so-called stereoactive stereoactive electron lone pair occurs. Such electron lone pair occurs. Such
distortions are common for main group ions with their valence s electrons ( distortions are common for main group ions with their valence s electrons (Tl Tl
+ +
, Bi , Bi
3+ 3+
, ,
Sn Sn
2+ 2+
, Sb , Sb
3+ 3+
, etc.). This distortion is similar to the one seen in NH , etc.). This distortion is similar to the one seen in NH
3 3
. .
Cyclic Cyclic Polyenes Polyenes
Benzene (C Benzene (C
6 6
H H
6 6
) )
Cyclobutadiene Cyclobutadiene (C (C
4 4
H H
4 4
) )
E
Consider two cyclic Consider two cyclic C C
n n
H H
n n
systems. The sketches to the systems. The sketches to the
left show the phases of the C left show the phases of the C
2p 2p
z z
orbitals orbitals that are responsible that are responsible
for for -interactions. In each -interactions. In each
system there are n system there are n -MOs. The -MOs. The
lowest energy orbital has no lowest energy orbital has no
nodes (all nodes (all orbitals orbitals in phase) while in phase) while
the highest energy state has the the highest energy state has the
maximum number (n/2). maximum number (n/2).
In C In C
6 6
H H
6 6
there is a large HOMO- there is a large HOMO-
LUMO gap and the e LUMO gap and the e
1g 1g
orbitals orbitals
are fully occupied. are fully occupied.
In C In C
4 4
H H
4 4
the the e e
g g
orbital HOMO is orbital HOMO is
occupied (triplet ground occupied (triplet ground
state). state).
1 1
st st
Order Jahn-Teller Distortion in C Order Jahn-Teller Distortion in C
4 4
H H
4 4
E
In practice In practice cyclobutadiene cyclobutadiene does not does not
form a regular square (D form a regular square (D
4h 4h
), but ), but
undergoes a distortion to a undergoes a distortion to a
rectangular shape (D rectangular shape (D
2h 2h
). This ). This
stabilizes one of the stabilizes one of the HOMOs HOMOs (which (which
becomes doubly occupied) and becomes doubly occupied) and
destabilizes the other (which destabilizes the other (which
becomes empty). becomes empty).
This leads to formation of two This leads to formation of two
localized double bonds. Hence, C localized double bonds. Hence, C
4 4
H H
4 4
is said to be is said to be antiaromatic antiaromatic. .
1 1
st st
Order Jahn-Teller Dist. Order Jahn-Teller Dist.
A non-linear molecule with an A non-linear molecule with an
incompletely filled degenerate incompletely filled degenerate
HOMO is susceptible to a structural HOMO is susceptible to a structural
distortion that removes the distortion that removes the
degeneracy. degeneracy.
Octahedral Coordination Octahedral Coordination
The diagram to the left shows a MO The diagram to the left shows a MO
diagram for a transition metal diagram for a transition metal
octahedrally coordinated by octahedrally coordinated by -bonding -bonding
ligands ligands. ( . ( -bonding has been neglected) -bonding has been neglected)
Note that in an octahedron there is no Note that in an octahedron there is no
mixing between s, p and d- mixing between s, p and d-orbitals orbitals. .
For a main group metal the same For a main group metal the same
diagram applies, but we neglect the d- diagram applies, but we neglect the d-
orbitals orbitals. .
The t The t
2g 2g
orbitals orbitals ( (d d
xy xy
, ,d d
yz yz
, ,d d
xz xz
) are ) are - -
antibonding antibonding (not shown), while the (not shown), while the
e e
g g
orbitals orbitals (d (d
z2 z2
,d ,d
y2-y2 y2-y2
) are ) are - -
antibonding antibonding. The latter are higher . The latter are higher
in energy since the spatial overlap in energy since the spatial overlap
of the of the -interaction is stronger. -interaction is stronger.
Square Planar Coordination Square Planar Coordination
The diagram to the left shows a MO The diagram to the left shows a MO
diagram for a transition metal in square diagram for a transition metal in square
planar coordination. ( planar coordination. ( -bonding has been -bonding has been
neglected) neglected)
Among the changes the most important is Among the changes the most important is
that now the s and d that now the s and d
z2 z2
orbitals orbitals can mix, can mix,
which stabilizes the d which stabilizes the d
z2 z2
and removes the and removes the
degeneracy of the degeneracy of the e e
g g
orbitals orbitals. .
Transition metals with electron counts that Transition metals with electron counts that
lead to partially filled lead to partially filled e e
g g
orbitals orbitals (HS d (HS d
4 4
, d , d
8 8
& d & d
9 9
in particular) will be prone to undergo in particular) will be prone to undergo
distortions from octahedral toward square distortions from octahedral toward square
planar. planar.
The d The d
8 8
ions Pd ions Pd
2+ 2+
and Pt and Pt
2+ 2+
have a strong have a strong
preference for sq. planar coordination, but preference for sq. planar coordination, but
with Ni with Ni
2+ 2+
the crystal field splitting is usually the crystal field splitting is usually
too small to overcome the spin pairing too small to overcome the spin pairing
energy and octahedral coordination results. energy and octahedral coordination results.
Jahn-Teller Distortions: Jahn-Teller Distortions:
The long and the short of it. The long and the short of it.
The Jahn-Teller theorem tells The Jahn-Teller theorem tells
us there should be a distortion us there should be a distortion
when the when the e e
g g
orbitals orbitals of a TM of a TM
octahedral complex are partially octahedral complex are partially
occupied, but it doesnt tell us occupied, but it doesnt tell us
what type of distortion should what type of distortion should
occur. occur. To a first approximation To a first approximation
two choices give the same two choices give the same
energetic stabilization. energetic stabilization.
2 long + 4 short bonds 2 long + 4 short bonds
stabilizes the d stabilizes the d
z2 z2
orbital orbital
2 short + 4 long bonds 2 short + 4 long bonds
stabilizes the d stabilizes the d
x2-y2 x2-y2
orbital orbital
. .
Distortions in d Distortions in d
9 9
& d & d
10 10
Halides Halides
In practice Cu In practice Cu
2+ 2+
(d (d
9 9
) and Mn ) and Mn
3+ 3+
(HS) almost always take the (HS) almost always take the 2 long + 4 2 long + 4
short short distortion distortion, and the distortions are usually considerably larger , and the distortions are usually considerably larger
with Cu with Cu
2+ 2+
. In contrast d . In contrast d
10 10
ions, such as Hg ions, such as Hg
2+ 2+
adopt very large adopt very large 2 short + 2 short +
4 long distortions 4 long distortions (in many cases the distortion is so large that the (in many cases the distortion is so large that the
coordination is essentially linear). For example consider the bond coordination is essentially linear). For example consider the bond
distances in CuBr distances in CuBr
2 2
(4 (4 2.40 2.40 , , 2 2 3.18 3.18 ) and HgBr ) and HgBr
2 2
(4 (4 3.23 3.23 , , 2 2
2.48 2.48 ), both of which adopt distorted CdI ), both of which adopt distorted CdI
2 2
structures. structures. Why is this Why is this
so? Why do d so? Why do d
10 10
ions distort at all? ions distort at all?
Short bonds drawn with
solid lines.
Long bonds drawn
with dotted lines.
Jahn-Teller Distortions d Jahn-Teller Distortions d
z2 z2
-s Mixing -s Mixing
The empty The empty n ns orbital is of s orbital is of
appropriate symmetry to mix with appropriate symmetry to mix with
the ( the (n-1 n-1)d )d
z2 z2
orbital, but not with orbital, but not with
the ( the (n-1 n-1)d )d
x2-y2 x2-y2
orbital. This orbital. This
dictates the details of the dist. dictates the details of the dist.
d d
9 9
case (Cu case (Cu
2+ 2+
): The d ): The d
z2 z2
-s mixing -s mixing
favors preferential occupation of favors preferential occupation of
the d the d
z2 z2
orbital (2 long + 4 short orbital (2 long + 4 short
favored) favored)
d d
10 10
case (Hg case (Hg
2+ 2+
): The d ): The d
z2 z2
-s mixing -s mixing
is largest when the energy is largest when the energy
separation between the two is separation between the two is
minimized ( minimized ( E E
2 2
> > E E
1 1
). (2 short + ). (2 short +
4 long favored) 4 long favored)