Documentos de Académico
Documentos de Profesional
Documentos de Cultura
Bonding and
Molecular Structure:
Orbital Hybridization
and Molecular Orbitals
Jeffrey Mack
California State University,
Sacramento
Orbitals & Theories of Chemical
Bonding
• Chapter 6 told us that the location of the valence
electrons in an atom is described by an orbital
model.
• It should seem reasonable that an orbital model
can also be used to describe electrons in
molecules.
• In this chapter, you will explore two common
approaches to rationalizing chemical bonding
based on orbitals:
• Valence Bond (VB) theory and Molecular Orbital
(MO) theory.
Valence Bonding Theory
Developed by Linus Pauling
• Premise: Bonding involves
valence electrons.
• Half-filled atomic orbitals on
bonding atoms overlap to
form bonds.
• Bonds are localized between
atoms (or as lone pairs). Linus Pauling, 1901-1994
• Leads to prediction of
molecular shape.
Molecular Orbital Theory
Developed by Robert S. Mullikan (1896-1986)
• Bonding electrons reside in Molecular Orbitals that
arise from the original atomic orbitals of the bonding
atoms.
• Bonding electrons are spread over the entire
molecule. (delocalized)
• Explains paramagnetism and electronic
spectroscopy in molecules.
*1s
1s 1s
1s
The Orbital Overlap Model of
Bonding
In H2 a sigma
() covalent
bond that arises
from the
overlap of two
half filled s
Overlap of two orbitals, one
s orbitals from each
atom.
Two s
orbitals
overlap
Overlap
of an s &
p orbital
Two p
orbitals
overlap
Valence Bond Theory
The main points of the valence bond approach to
bonding are:
• Orbitals overlap to form a bond between two atoms.
• Overlapping orbitals hold two electrons of opposite
spin. Usually, one electron is supplied by each of
the two bonded atoms.
• The bonding electrons are localized with a higher
probability of being found within a region of space
between the bonding nuclei. Both electrons are
simultaneously associated with both nuclei.
Valence Bond Terminology
Overlap: two orbitals existing in the same region of space
lp: lone pair of electrons (non-bonding)
bp: bonding pair of electrons (result of orbital overlap)
Central atom: the atom of concern in a molecule
hybridization: the linear combination of atomic orbitals
hybrid orbital: bonding orbitals that arise from the mixing of AO’s.
-bond: (sigma bond) overlap of orbitals along the bond axis
-bond: (pi bond) overlap of orbitals above and below the bond
axis.
single bond: one -bond
double bond: one -bond & one -bond
triple bond: one -bond & two -bonds
Sigma (σ) Bonding
When bonding occurs along a bond axis, it is
referred to as a “sigma” bond: ()
X : Y
:
X Y
:
X : Y
consider carbon as a
central atom in a 2p
molecule:
The valence orbitals
are the 2s & 2p’s
There are 4 valence 2s
electrons:
carbon
Hybridization of Atomic Orbitals
This hybridization determines by the electron pair geometry
for the central atom.
Each half-filled orbital is capable of
forming a covalent bond.
The new orbitals
2p are called
sp3
carbon Valence
bond orbitals
2s
carbon
The 4 valence electrons on carbon fill the orbitals by Hund’s
rule:
Hybridization of Atomic Orbitals
Bonding in methane involves the overlap of the new sp3
hybrid orbitals in carbon with the 1s orbitals in hydrogen.
H
H H
H
2
p
sp3 hybrid valence
Carbon bond orbitals.
2s
Each overlap contains two shared
electrons, one from each bonding nuclei.
Each overlap results in a –bond
Bonding in CH4
sp3 Hybridization
Since there are four sp3 hybrid orbitals, they must spread out to
form a tetrahedron about a central atom to minimize repulsion.
It follows then that an central atom that has a “tetrahedral”
EPG must have sp3 hybridization.
sp3 Hybridization
Water must also bond via sp3 hybrid valence bond
orbitals.
Bonding in a Tetrahedron Formation
of Hybrid Atomic Orbitals
4 C atom orbitals
hybridize to form
four equivalent sp3
hybrid atomic
orbitals.
Bonding in a Tetrahedron Formation
of Hybrid Atomic Orbitals
4 C atom orbitals
hybridize to form four
equivalent sp3 hybrid
atomic orbitals.
sp3 Hybridization
Conclusion:
When the central atom in a molecule has
combination of 4 total sigma (single) bonds and
lone pairs, the hybridization at the central atom
is sp3.
sp2 Hybridization
In order to attain the needed geometry, the atomic orbitals
(AO’s) mix or hybridize to form new valence bond orbitals.
The 2s & two of the 2p orbitals mix:
there is one
2p p-orbital left
The new hybrid over
obitals all have the
same energy: sp2
The left over p-orbital can form a -bond with another half-
filled p-orbital.
The left over p-orbital can form a -bond with another half-
filled p-orbital.
2p 2p
sp hybrid valence bond
Carbon orbitals form.
2s
sp Hybridization
Just as with sp2 hybridization, in sp hybridization, the left over
p-orbitals can form -bonds (in this case 2).
In acetylene (C2H2) there is a triple bond. (1 , 2 ’s)
and Bonding in C2H2
sp Hybridization
Other examples of molecules with sp hybridization are:
0… s-orbitals
At n = 3 l= 1… p-orbitals
2… d-orbitals
We’ve seen that when four sp3 hybrid orbitals form, a central
atom can accommodate only up to 8 electrons in the valence
(bp & lp).
To place more electrons in the valence, we must bring the d–
orbitals into the “mix”.
Consider a Molecule Like PCl5
Phosphorous:valence electron configuration
of 3s23p3. (5 electrons)
Each of the five electrons forms a single bond
with a chlorine atom.
3d 3d
3p new sp3d hybrid valence
bond orbitals
mix the 3s, the
three 3p and one
3d
3s
Each of these half–filled sp3d
orbitals can form a –bond with a
chlorine atom in PCl5.
Additional example of sp3d hybrid
molecules:
SF4 (sulfur tetrafluoride) ClF3 (chlorine trifluoride)
3d 3d
3d 3d
3p six new sp3d2 hybrid
valence bond orbitals
mix the 3s, the
three 3p and two
3d’s Each of these half–filled
3s sp3d2 orbitals can form a
–bond with a fluorine
sulfur atom.
sp3d2 Hybridization: SF6
SF6
Predicting Hybridization
1. Start by drawing the Lewis structure (check
formal charges)
2. Use VSEPR theory the electron group
geometry about the central atom.
3. Relate the central atom electron group
geometry to the corresponding hybridization.
4. Identify and label the orbital overlap in each
bond.
5. Label the bonds with and bonds.
Hybridization Practice
• Indicate the central atom hybridization for the
following.
XeF4
CH2O
BrF5
SF6
Br3
Additional Examples of sp3d2
s1s*
Energy
1s 1s
s1s
1s 1s
H-atom H-atom
2 electrons in a bonding MO
1s
# of Bonding electrons - # antibonding electrons 2-0
BO = = =1
2 2
Bond Order = 1 (single bond)
*1s
What happens to a H2 molecule
if one of the electrons is excited
1s 1s
to the anti-bonding orbital?
H-atom H-atom
1s
2-0
Original BO = =1 ground state H2
2
*1s
1s 1s
The molecule falls
1- 1
1s New BO = = 0 apart!
2
excited state H2 Photodissociation
Why Doesn’t He2 Exist?
electrons in AO’s
*1s fill the MO’s
He: 1s2
1s 1s
1s
p*2p
2p 2p
s 2p
The two 2p and the
p2p two 2* p are degenerate.
p*2p
2p 2p
p2p
s 2p
2p
MO’s
2s
MO’s
1s
MO’s
*1s
1s
Bonding in O2
Since the 1s and 2s MO’s are full, they do not contribute any
net bonding Any net bonding will be determined by the 2p
MO’s.
Each O–atom has four 2p s*2p
electrons:
p*2p
2p 2p
O - atom O - atom
p2p
s 2p
The electrons fill the MO’s fill by the Aufbau principle and Hund’s
rule.
Bonding in O2
Since the 1s and 2s MO’s are full, they do not contribute any
net bonding Any net bonding will be determined by the 2p
MO’s.
s*2p
Each O–atom has four 2p
electrons:
p*2p
2p 2p
O - atom O - atom
p2p
s 2p
The electrons fill the MO’s fill by the Aufbau principle and Hund’s
rule
Bonding in O2
6-2
BO = =2 double bond
2
This agrees with the Lewis dot structure: O=O
s*2p
p*2p
2p 2p
O - atom
p2p O - atom
s 2p However, VB theory did not
tell us that the molecule is
paramagnetic!
The Paramagnetism of O2
(c) Paramagnetic liquid O2 clings to a magnet. (d) Diamagnetic liquid N2 is not attracted to a
magnet.