Chemistry 120
Molecular Structure
Both atoms and molecules are quantum systems
We need a method of describing molecules in a quantum mechanical way so that we can predict structure and properties
The method we use is the
Linear Combination of Atomic Orbitals
where we can use the properties of atoms to predict the properties of molecules.
Chemistry 120
Molecular Structure
We combine atoms to form molecules by considering the phase of the atomic orbitals we are using
We represent the phase via the shading we give the orbital.
The phase represents the sign of the wavefunction
Chemistry 120
Molecular Structure
We combine atoms to form molecules by considering the phase of the atomic orbitals we are using
The phase represents the sign of the wavefunction
We represent the phase via the shading we give the orbital.
Chemistry 120
Molecular Structure
For an s orbital, the orbital has the same phase everywhere:
For a p orbital, there is a
change in the sign of the
wavefunction across the
nodal plane:2p orbital, n = 2, l = 1, ml = -1
1s orbital, n = 1, l = 0
Chemistry 120
Molecular Structure
Consider two H atoms (1s1) coming together from infinite separation.
There are two possibilities:
1 The wavefunctions are in phase
2 The wavefunctions are not in phase
Chemistry 120
Molecular Structure
Case 1: The wavefunctions are in phase
The atoms move together and the electron waves overlap with the same phase, producing constructive interference and a build up of electron density between the nuclei
The energy of the system drops and we form a bond
Chemistry 120
r = 8 Å
r = 7 Å
r = 6 Å
r = 5 År = 0.75 Å
r = 1 Å
r = 2 Å
r = 3 Å
Chemistry 120
Molecular Structure
Case 2: The wavefunctions are out of phase
The atoms move together and the electron waves have opposite phase.
The electron waves overlap producing destructive interference and electron density between the nuclei is reduced.
The energy of the system rises and we have an antibonding situation
Chemistry 120
r = 8 Å
r = 7 Å
r = 5 Å
r = 4 Å r = 0.75 Å
r = 1 Å
r = 2 Å
r = 3 Å
Chemistry 120
Bonding Antibonding
Two atoms with wavefunctions in phase overlap with constructive interference. Electron density increases between the nuclei and the overall energy decreases.
When the wavefunctions are of opposite phase, the electron density between the nuclei decreases due to destructive interference. The energy of the system rises and we have an antibonding situation
Chemistry 120
Bonding
Antibonding
Chemistry 120
Organic Structure and Bonding
Review of diatomic bonding
There are two types of bond that are important in this part of the Periodic Table
bonds and bonds
B5
C6
N7
O8
F9
Si14
P15
S16
Cl17
Se34
Br35
I53
Chemistry 120
Organic Structure and Bonding
bonds and bonds
bonds are in general stronger than bonds and can be formed from either s or p orbitals:
Chemistry 120
Organic Structure and Bonding
bonds and bonds
bonds have no nodal plane that contains the two nuclei.
The * antibonding orbital has a nodal plane between the two nuclei
Chemistry 120
Organic Structure and Bonding
bonds and bonds
bonds have a nodal plane that contains both nuclei,
The * antibonding orbital also has a plane between the nuclei
Chemistry 120
Organic Structure and Bonding
bonds and bonds
These , bonding orbitals and *, * antibonding orbitals are the orbitals that are used to bind all simple organic molecules together.
We can also describe the bonding in diatomic molecules
important models for larger organic systems
Chemistry 120
Organic Structure and Bonding
bonds and bonds
To describe the bonding in the diatomic molecules such as O2, N2 and X2 (X = F, Cl, Br and I), we use both the s orbitals and the p orbitals on the two atoms as a basis set - the palette of atomic orbitals from which we will build the molecular orbitals.
The energies of the two different l states, s and p, are slightly different in polyelectronic atoms.
Chemistry 120
Organic Structure and Bonding
bonds and bonds
The s orbitals and the p orbitals appear as follows
Chemistry 120
Organic Structure and Bonding bonds and bonds
We arrange the atoms along one of the axes for convenience and so the first pair of orbitals we construct are the s and s* orbitals from the s orbitals on the atoms.
Chemistry 120
Organic Structure and Bonding bonds and bonds
We now us the higher energy p orbitals to construct p and porbitals
Chemistry 120
Organic Structure and Bonding bonds and bonds
The complete molecular orbital diagram for all the diatomic molecules from Li2 to N2
Chemistry 120
Organic Structure and Bonding bonds and bonds
The complete molecular orbital diagram for all the diatomic molecules from Li2 to N2
As each molecule has a different number of electrons,
Li2 2 Be2 4 B2 6 C2 8
N2 10 O2 12 F2 14 Ne2 16
Chemistry 120
Organic Structure and Bonding bonds and bonds
Li2 2 Be2 4 B2 6 C2 8
N2 10 O2 12 F2 14 Ne2 16
We can write the electronic structure of each molecule by placing electron pairs into the orbitals.
Chemistry 120
Organic Structure and Bonding bonds and bonds
Li2 2 Be2 4 B2 6 C2 8
N2 10 O2 12 F2 14 Ne2 16
Something peculiar happens after N2
Recall that as the charge on the nucleus increases, the orbitals become more stabilized and the electrons become more strongly bound.
Chemistry 120
Organic Structure and Bonding bonds and bonds
Li2 2 Be2 4 B2 6 C2 8
N2 10 O2 12 F2 14 Ne2 16
This happens by different amounts, depending on the orbital.
After N2 (10 e-), the ordering of the orbitals derived from p change their order in the molecule
Chemistry 120
Organic Structure and Bonding bonds and bonds
For N2 (10 e-), the ordering is this
For O2 (12 e-), the ordering is this
Chemistry 120
Organic Structure and Bonding bonds and bonds
This is an example of configurational interaction
Each electron moves in the field of the other electrons. If the energies of the two molecular orbitals are sufficiently close and the nodal properties are correct, molecular orbitals will interact and shuffle their energies in the molecule.
This causes the orbitals to change their energetic ordering but only when the nuclear charge is high enough to force the electrons close in energy.
Chemistry 120
Organic Structure and Bonding bonds and bonds
Configurational interaction
Each electron moves in the field of the other electrons. If the energies of the two molecular orbitals are sufficiently close and the nodal properties are correct, molecular orbitals will interact and shuffle their energies in the molecule.
This causes the orbitals to change their energetic ordering but only when the nuclear charge is high enough to force the electrons close in energy.
Chemistry 120
Molecular Structure
A full description of the structure of a molecule requires the solution of the Schrödinger equation for the entire molecule.
The potential term is far too complicated to be solved analytically and so we need an empirical approach to molecular structure.
ErVT
EH
,,ˆˆ
ˆ
,,ˆ rV
Chemistry 120
Molecular Structure
There are two common approaches
- Lewis description
- Valence Shell Electron Pair Repulsion (VSEPR)
theory
and both are based on the electron count at the central atom of the molecule or fragment of the molecule.
Chemistry 120
Molecular Structure
Lewis description
The covalent chemical bond can be thought of as a pair of electrons shared between atoms;By considering the number of electrons in the valence shell and the number of electrons in the outer atoms, we can explain the presence of lone pairs and the gross structure of the molecule.
G. N. Lewis
Chemistry 120
Molecular Structure
Lewis description
The covalent chemical bond can be thought of as a pair of electrons shared between atoms;
By considering the number of electrons in the valence shell and the number of electrons in the outer atoms, we can explain the presence of lone pairs and the gross structure of the molecule in simple cases.
G. N. Lewis
Chemistry 120
Molecular Structure
Lewis description
The Lewis description arose form an attempt to cram the observed properties of atoms in combination into a mechanically classical picture of the physical world then prevalent; in fact even classically, the structure of the atom was not explicable.
G. N. Lewis
http://www.chem.yale.edu/~chem125/125/history99/7BondTheory/LewisOctet/
cubicoctet.html
Chemistry 120
Molecular Structure
Lewis description
The Lewis description is based on the observed requirement that the atom achieves the valence shell octet associated with the noble gases - a noble gas configuration.
Consider the formation of MgCl2
Mg: 1s22s22p63s2 or [Ne]3s2
Cl: 1s22s22p63s23p5 or [Ne]3s23p5
Chemistry 120
Molecular Structure
Lewis description
We know that MgCl2 is ionic and so the changes in the valence shell configurations are
Mg: 1s22s22p63s2 or [Ne]3s2
Mg2+: 1s22s22p6 or [Ne]
Cl: 1s22s22p63s23p5 or [Ne]3s23p5
Cl-: 1s22s22p63s23p6 or [Ne]3s23p6 (i.e. [Ar])
Chemistry 120
Molecular Structure
Lewis description
We therefore account for the stability of MgCl2 through the formation of closed shell ions with noble gas configurations, namely
Mg2+: 1s22s22p63s2 or [Ne]
and
Cl-: 1s22s22p63s23p5 or [Ne]3s23p6 (i.e. [Ar])
Chemistry 120
Molecular Structure
Lewis description
In this respect, the Lewis description of bonding is accurate, but there are major failures with molecules.
Lewis described molecular structure through the idea that the atom had some inherent tetrahedral quality and that the electrons were distributed in static manner at the vertices of the tetrahedron
Chemistry 120
Molecular Structure
Lewis description
Lewis described molecular structure through the idea that the atom had some inherent tetrahedral structure and that the electrons were distributed in static manner at the vertices of the tetrahedron.
Chemistry 120
Molecular Structure
Lewis description
Molecular species therefore take structures via sharing electrons through the vertices of the tetrahedron. This naturally implies that all molecules are tetrahedral, which causes major problems for those that are not……….
Chemistry 120
Molecular Structure
Lewis description
Examples: BH3, CH4, NH3, OH2 and FH
All these structures are based on the tetrahedron and the sharing of electrons in bonds or the presence of lone pairs at the corner of the tetrahedron.
Chemistry 120
Molecular Structure
Lewis description
Examples: BH3, CH4, NH3, OH2 and FH
We can depict the valence shell (i.e. the shell with the highest principle quantum number) as
B C N O F
1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5
Chemistry 120
Molecular Structure
Lewis description
Examples: BH3, CH4, NH3, OH2 and FH
We satisfy the open valences of these atoms with H atoms :
B C N O F
1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5
H
Chemistry 120
Molecular Structure
Examples: BH3, CH4, NH3, OH2 and FH
B
1s22s22p1
3H
B
H
H
H
1s22s22p4
C
1s22s22p2
4H
C
H
H
H
H
1s22s22p6
N
1s22s22p3
3H
NH
H
H
1s22s22p6
O
1s22s22p4
2H
OH
H
1s22s22p6
F
1s22s22p5
1H
F H
1s22s22p6
Chemistry 120
Molecular Structure
Examples: BH3, CH4, NH3, OH2 and FH
B
H
H
H
C
H
H
H
H NH
H
H OH
H
F H
HB
HH H
C
H
HH H
NHH
OHH
F
H
Chemistry 120
Molecular Structure
Examples: BH3, CH4, NH3, OH2 and FH
B
H
H
H
C
H
H
H
H NH
H
H OH
H
F H
HB
HH H
C
H
HH H
NHH
OHH
F
H
Chemistry 120
Molecular Structure
Examples: BH3, CH4, NH3, OH2 and FH
The structures of the first row hydrides are not accurately predicted by the Lewis Theory of structure and bonding.
HB
HH H
C
H
HH H
NHH
OHH
F
H
Chemistry 120
Molecular Structure
VSEPR
The other model for molecular structure is VSEPR.
We consider a closed shell atom and we also assume that it is spherical. The structure is then determined by the number of “stereochemically active units” present in the outer shell.
These stereochemically active units are the ‘lone pairs’ and the bond pairs that are formally assumed to exist in a molecule from a Lewis picture of structure and bonding.
Chemistry 120
Molecular Structure
VSEPR
Once we assume that bond and lone pairs exist, we introduce some other assumptions, one about structure and one about energies of interactions.
The structural types that we use are based on the distribution of points on the surface of a sphere such that the distance between them is a maximum.
Chemistry 120
Molecular Structure
VSEPR
For two stereochemically active units, the obvious geometry is linear:
Chemistry 120
Molecular Structure
VSEPR
For three stereochemically active units, we form a triangular arrangement of atoms around the central atom:
This geometry is termed
Trigonal Planar
Chemistry 120
Molecular Structure
VSEPR
Four stereochemically active units are arranged in the form of a tetrahedron
Chemistry 120
Molecular Structure
VSEPR
For five stereochemically active units, there are two choices. The one most commonly encountered is the trigonal bipyramid
Chemistry 120
Molecular Structure
VSEPR
Six stereochemically active units have only one choice for the base geometry – the octahedron
Chemistry 120
Molecular Structure
VSEPR
In each of these geometries, the sites that are predicted are occupied either by an atom or by an ‘electron pair’
The final requirement is to detail the interaction between these various pairs of electrons – bond and lone – in the atom.
Chemistry 120
Molecular Structure
VSEPR
The interaction energies that we are interested in are the repulsions between these pairs of electrons.
As bond pairs are more tightly confined, the reulsions due to bond pairs are less. Lone pairs, assumed to be more diffuse, suffer from higher repulsions and thus the energy ordering is:
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Chemistry 120
Molecular Structure
VSEPR
With these rules in hand, and a knowledge of the possible geometries, we can now predict with some certainty the expected molecular geometry of any main group species.
Chemistry 120
Molecular Structure
VSEPR
Example: What are the structures of SF4, CF4 and XeF4?
Step 1: Count the electrons on each central metal atom.
S 6 C 4 Xe 8
Chemistry 120
Molecular Structure
VSEPR
Example: What are the structures of SF4, CF4 and XeF4?
Step 1: Count the electrons on each central metal atom.
S 6 C 4 Xe 8
Step 2: Determine the number of bond pairs that each atom has.
In this case it is 4 each.
Chemistry 120
Molecular Structure
VSEPR
Example: What are the structures of SF4, CF4 and XeF4?
Step 3: Determine the number of ‘lone pairs’ that each atom has. As each bond has 1 e- from the central atom, then the number of electrons in lone pairs is just
S 6 - 4 = 2 C 4 - 4 = 0 Xe 8 - 4 = 4
Chemistry 120
Molecular Structure
VSEPR
Example: What are the structures of SF4, CF4 and XeF4?
Step 4: Determine the number of sterochemically active species by type
SF4 4 bond pairs, 1 lone pair
CF4 4 bond pairs, 0 lone pair
XeF4 4 bond pairs, 2 lone pairs
Chemistry 120
Molecular Structure
VSEPR
Example: What are the structures of SF4, CF4 and XeF4?
Step 5: Apply the energy rules to each structure type and determine the structure type
SF4 trigonal bipyramid
CF4 tetrahedron
XeF4 octahedron
Chemistry 120
Molecular Structure
VSEPR
Example: What are the structures of SF4, CF4 and XeF4?
And so the structures are……..
S
F
F
F
F
F XeF
F
F
C
F
F
F
F
Chemistry 120
Molecular Structure Review
• Lewis electron dot structures
• Valence Shell Electron Pair Repulsion (VSEPR)
theory
Both are based on the electron count at the central atom, A, of the molecule or fragment of the molecule AXn.
Chemistry 120
We observe that the atoms achieve a noble gas configuration in the valence shell, often (but not always) an octet.
The first three noble gas configurations:
[He]: 1s2 2 valence electrons
[Ne]: 1s22s22p6 8 valence electrons
[Ar]: 1s22s22p63s23p6 8 valence electrons
Molecular Structure Review
Chemistry 120
Molecular Structure Review
Li
H
Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Os Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Ru Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra
He
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np Pu Bk Cf EsCmAm Fm Md No Lr
Rf Db Bh MtAc Sg Hs
Chemistry 120
AHn Examples:
BH3, CH4, NH3, OH2 and FH
We satisfy the open valences of these atoms with H atoms :
H
Molecular Structure Review
B C N O F
[He] 2s22p1 [He] 2s22p2 [He] 2s22p3 [He] 2s22p4 [He] 2s22p5
Chemistry 120
Molecular Structure Review
Li
H
Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Os Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Ru Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra
He
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np Pu Bk Cf EsCmAm Fm Md No Lr
Rf Db Bh MtAc Sg Hs
Chemistry 120
AHn: BH3, CH4, NH3, OH2 and FH
Molecular Structure Review
B
[He]2s22p1
3H
B
H
H
H
[He]2s22p4
C
[He]2s22p2
4H
C
H
H
H
H
[He]2s22p6
[Ne]
or
N
3H
NH
H
H
[He]2s22p6
[Ne]
or
[He]2s22p3
O
[He]2s22p4
2H
OH
H
[He]2s22p6
[Ne]
or
F
[He]2s22p5
1H
F H
[He]2s22p6
[Ne]
or
Chemistry 120
VSEPR: What are the structures of BH3, CH4, NH3, OH2, and FH?
Step 1: Count the electrons on each central atom.
B 3 [He]2s22p1
C 4 [He]2s22p2
N 5 [He]2s22p3
O 6 [He]2s22p4
F 7 [He]2s22p5
Molecular Structure Review
Chemistry 120
Step 2: Determine the number of bond pairs for each central atom.
Molecular Structure Review
B
H
H
H
C
H
H
H
H NH
H
H OH
H
F H
3 4 3 2 1Number of bond pairs:
Chemistry 120
Step 3: Determine the number of ‘lone pairs’ remaining on the central atom.
Molecular Structure Review
B
H
H
H
C
H
H
H
H NH
H
H OH
H
F H
3 4 3 2 1
0 0 1 2 3
Number of bond pairs:
Number of lone pairs:
Chemistry 120
Step 4: Determine the total number of stereochemically active units (bond pairs and lone pairs of electrons).
BH3 3 bond pairs + 0 lone pairs = 3
CH4 4 bond pairs + 0 lone pairs = 4
NH3 3 bond pairs + 1 lone pair = 4
OH2 2 bond pairs + 2 lone pairs = 4
FH 1 bond pairs + 3 lone pairs = 4
Molecular Structure Review
Chemistry 120
Molecular Structure Review
Step 5: Determine the structure type by applying the energy rules to each structure type.
The most favorable structure minimizes steric interactions among the stereochemically active units.
For a molecule with a central atom (B), imagine the stereochemically active units (A) on the surface of a sphere as far apart in space as possible.
Chemistry 120
Molecular Structure Review
BA2 BA3 BA4
The number of stereochemically active units determines the geometry around the central atom.
linear trigonal planar tetrahedral
Chemistry 120
Molecular Structure Review
BA5 BA6
trigonal bipyramid octahedral
Chemistry 120
Which VSEPR geometry is appropriate for these compounds?
BH3 3 bond pairs + 0 lone pairs = 3
CH4 4 bond pairs + 0 lone pairs = 4
NH3 3 bond pairs + 1 lone pair = 4
OH2 2 bond pairs + 2 lone pairs = 4
FH 1 bond pairs + 3 lone pairs = 4
Molecular Structure Review
Chemistry 120
Molecular Structure Review
BH3 3 bond pairs + 0 lone pairs = 3
Chemistry 120
Molecular Structure Review
BH3 3 bond pairs + 0 lone pairs = 3
trigonal planar
Chemistry 120
Molecular Structure Review
CH4, NH3, OH2, FH: All have 4 stereochemically active units.
Chemistry 120
Molecular Structure Review
CH4, NH3, OH2, FH: All have 4 stereochemically active units.
tetrahedral
Chemistry 120
CH4, NH3, OH2 and FH
Molecular Structure Review
HC
H
HH
HN
HH
OHH
F
H
All have a tetrahedral geometry at the central atom.
Chemistry 120
Molecular Structure Review
Q: If there are a mix of bonding pairs and lone pairs around the central atom, what determines their positions?
Chemistry 120
Molecular Structure
A: As bond pairs are more tightly confined, the repulsions due to bond pairs are less. Lone pairs, assumed to be more diffuse, suffer from higher repulsions and thus the energy ordering is:
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Q: If there are a mix of bonding pairs and lone pairs around the central atom, what determines their positions?
Chemistry 120
Molecular Structure
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Examples :
PCl5 PCl3
Chemistry 120
Molecular Structure
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Examples :
PCl5 PCl3
Cl PCl
Cl
Cl
Cl
Chemistry 120
Molecular Structure
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Examples :
PCl5 PCl3
Cl PCl
Cl
Cl
ClCl
PClCl
AB5 AB4
Chemistry 120
Molecular Structure
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Examples :
SF2 SF4
Chemistry 120
Molecular Structure
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Examples :
SF2 SF4
SFF
Chemistry 120
Molecular Structure Review
Trigonal Bipyramid
Ae B
Ae
Ae
Aa
Aa
120
90
e
Chemistry 120
Molecular Structure
B.P.-B.P. < B.P.-L.P. < L.P.-L.P
Examples :
SF2 SF4
SFF
F SF
F
F
Chemistry 120
Molecular Structure Review
Q: What if the species is charged, e.g. PH4+ ?
Chemistry 120
Molecular Structure Review
Q: What if the species is charged, e.g. PH4+ ?
A: Take the charge into account in the valence electrons of the central atom.
P0 5 valence electrons
P+ 4 valence electrons
Chemistry 120
Molecular Structure Review
Q: What if the species is charged, e.g. PH4+ ?
A: Take the charge into account in the valence electrons of the central atom.
P0 5 valence electrons
P+ 4 valence electrons
HP
H
HH
Chemistry 120
Molecular Structure Review
Q: If there are three different atoms in a molecule, which one is the central one?
Chemistry 120
Molecular Structure Review
Q: If there are three different atoms in a molecule, which one is the central one?
Chemistry 120
Molecular Structure Review
Q: If there are three different atoms in a molecule, which one is the central one?
A: The least electronegative atom (most electropositive atom) is in the center.
Chemistry 120
Molecular Structure Review
Q: If there are three different atoms in a molecule, which one is the central one?
A: The least electronegative atom (most electropositive atom) is in the center.
Example:
COCl2
Chemistry 120
Molecular Structure Review
Q: If there are three different atoms in a molecule, which one is the central one?
A: The least electronegative atom (most electropositive atom) is in the center.
Example:
COCl2
O
C
Cl Cl
Chemistry 120
Organic Structure and Bonding
Organic chemistry is the chemistry of the top right corner of the Periodic table.
It is the branch of chemistry that is most closely connected to biology and health-related science:
Medicine and Pharmaceuticals
The key elements are carbon, hydrogen, oxygen, nitrogen and phosphorous.
Chemistry 120
Organic Structure and Bonding and review
bonds: No nodal plane that contains both nuclei
bonds: 1 nodal plane that contains both nuclei
Chemistry 120
Organic Structure and Bonding
Bonding in organic molecule almost always only contains these two types of bond.
In organic molecules, neutral carbon atoms always have 4 and only 4 bonds:
They can be single, double or triple
Chemistry 120
H
HH
H
HH
Alkyne: 2-butyne single and triple bonds
H
H H
H
H H
Alkene: 2-butene single and double bonds
H H
H
H H
H
HH
Alkane: butane all single bonds
H
H
H
H
Bonding in organic molecule almost always only contains these two types of bond.
In organic molecules, neutral carbon atoms always have 4 and only 4 bonds:
They can be single, double or triple
Organic Structure and Bonding
Chemistry 120
In methane, all the bonds are identical and methane is tetrahedral.
How do we describe the bonding in methane?
Two methods:
1. Full molecular orbital theory
needs group theory and quantum mechanics
2. Hybridization of atomic orbitals
an approximation that works well in organic chemistry
Organic Structure and Bonding
Chemistry 120
This is a method for describing the bonding in organic molecules by adding all of the wavefunctions together on a single carbon atom, using the three 2p orbitals and the 2s orbital.
We can form three different combinations:
sp3 sp2 sp
where the superscripts show the number of p orbitals that we are adding to the s orbital
Hybridization
Chemistry 120
In terms of energy, sp3 hybridization looks like:
sp3 hybridization
Chemistry 120
The four sp3 hybrid orbitals point naturally at the corners of the tetrahedron.
Carbon is tetrahedrally coordinated
All are equal in length and the angle between the orbitals and therefore the bonds is ~ 109.5°
Carbon atoms with four single bonds are sp3 hybridized
sp3 hybridization
Chemistry 120
We can also add two p orbitals to the s orbital to form an sp2 hybrid, leaving one p orbital unused
sp2 hybridization
2s
2p
Hybridize
three sp2 hybrids
Atom Hybridized atom
Chemistry 120
The three sp2 hybrid orbitals point naturally at the corners of a triangle – the coordination at carbon is trigonal planar. All are equal in length and the angle between the orbitals and therefore the bonds is 120°
Carbon atoms with two single bonds and one double bond are sp2 hybridized
sp2 hybridization
Chemistry 120
The double bond can occur due to the p orbital that we have not used on the carbon atom:
sp2 hybridization
Chemistry 120
Imagine two sp2 hybridized carbon atoms forming a bond using one sp2 hybrid:
The ‘spare’ p orbitals can then form the bond.
sp2 hybridization
Chemistry 120
Alkenes, ketones, aldehydes, and any double bonded atom are all sp2 hybridized. The bonds are formed from the hybrids and the bond from the p orbital left over on each atom.
sp2 hybridization
Chemistry 120
The last possible hybrid is the sp hybrid. We use one p orbital and 1 s orbital:
sp hybridization
Chemistry 120
The two sp hybrids point at 180° to each other.
The two p orbitals can form two bonds
sp hybridization
Chemistry 120
Any triple bonded atom is sp hybridized
Alkynes, CO and CN- are all triply bonded.
sp hybridization
Chemistry 120
In a alkene, or other double bonded structure, the sp2 hybrids from the framework
Double and Triple bond structures
The bond between carbon atoms contains 4 electrons, two in an sp2 bond and two in the p bond
Chemistry 120
In a alkyne, or other triple bonded structure, the sp hybrids from the framework
Double and Triple bond structures
The bond between carbon atoms contains 6 electrons, two in an sp bond and four in the two p bonds
Chemistry 120
So far, we have considered bonds between identical atoms – homoatomic bonds.
The electron distributions are equal as the orbitals on the atoms have identical energies and sizes.
In a heteroatomic system, this is not true and the atomic orbitals that make up the molecular orbitals have different energies.
Polar and non-polar bonds
Chemistry 120
The orbital energies on an electronegative atom are lower in energy and therefore stabilize an electron more effectively.
In a heteroatomic bond, this causes a small change in the distribution of the bonding electron density and thus a small, permanent charge difference
Polar and non-polar bonds
Chemistry 120
For a non-polar molecule, the molecular orbital diagram is the standard diagram for a diatomic, shown here for O2-F2
Polar molecules are skewed in energy.
Polar and non-polar bonds
Chemistry 120
Polar molecules are skewed in energy.
The bonding molecular orbitals are more similar to the lower energy atomic orbitals – those on the electronegative element.
The opposite is true for the antibonding orbitals.
Polar and non-polar bonds
Chemistry 120
Phase Changes
Matter exists primarily in three phases:
solid
liquid
gas
Both elements and compounds are found in
these three phases, and are denoted by
subscripts, e.g. N2 (g), H2O(l), and Au(s).
Chemistry 120
Phase Changes
The three phases interconvert with one another.
solidliquid
gas
Chemistry 120
Phase Changes
solidliquid
gas
condensationvaporization
Interconversions of gases and liquids are called:
Chemistry 120
Phase Changes
Interconversions of liquids and solids are called:
solidliquid
gas
melting
freezing
Chemistry 120
Phase Changes
Interconversions of gases and solids are called:
solidliquid
gas
sublimation deposition
Chemistry 120
Phase Changes
AB – sublimation/deposition AD – melting/freezing
AC – vaporization/condensation
Chemistry 120
Phase Changes
Changing from a less dense phase to a more dense phase (e.g. condensation) is exothermic. Changing from a more dense phase to a less dense (e.g. vaporization) one is endothermic.
For any two phases, the energy changes in both directions are equal in magnitude, but opposite in sign.
Hvap = -Hcon
Recall that enthalpy is a state function.
Chemistry 120
Phase Changes
H2O enthalpy of fusion (melting)
Chemistry 120
Phase Changes
Liquids and their vapors are in equilibrium.
Pressure of a vapors (gas phase)
= vapor pressure of liquid
Pressure and temperature are directly proportional.
Recall PV = nRT
Chemistry 120
Phase Changes
SCF = supercritical fluid
Chemistry 120
Phase Changes
AB – sublimation/deposition AD – melting/freezing
AC – vaporization/condensation
Chemistry 120
Phase Changes
The temperature at which a liquid boils is called its boiling point (bp). Boiling point is a function atmospheric pressure, or the pressure above the solution.
Normal boiling point is the boiling temperature of a liquid at 1 atmosphere (atm) pressure.
Chemistry 120
Phase Changes
Critical temperature, Tc, is the highest temperature at which liquid and vapor exist in equilibrium.
Critical pressure, Pc, is the vapor pressure at the critical temperature.
Critical point is reached at Tc and Pc.
Triple point is the temperature and pressure at which all three phases coexist.
Chemistry 120
Phase Changes
H2O phase diagram
C = Tc, Pc
A = triple point
Chemistry 120
Phase Changes
Phase diagram for HgI2 (mercuric iodide)
HgI2 () and HgI2 () are both solids but different phases.
Chemistry 120
The phase changes from solid to liquid to gas are governed by intermolecular forces.
Intramolecular forces are the chemical bonding forces discussed previously.
These intermolecular forces have both attractive and repulsive components. Collectively they are called van der Waals forces after the Dutch Nobel laureate (physics) who described them.
Intermolecular Forces
Chemistry 120
Intermolecular Forces
Johannes Diderik van der Waals
Van der Waals forces describe the behavior of a non-ideal gas, which includes both attractive and repulsive components.
[P + a(n/V)2](V-bn) = nRT
Chemistry 120
Intermolecular Forces
All molecules exert weak attractions on one another due to the mutual attraction of nuclei and electrons. These attractive forces are only significant at very short distances.
At such small distances the intermolecular repulsion of the electrons on different atoms is also significant.
Chemistry 120
Intermolecular Forces
The electrons orbiting all atoms and molecules can be perturbed by an electric field, with greater or lesser ease. This property is called polarizability.
The electron cloud around an atom or molecule can give an instantaneous dipole any time that the electrons are not distributed perfectly symmetrically.
Such a dipole can induce dipoles in other species nearby.
Chemistry 120
Intermolecular Forces
Chemistry 120
Intermolecular Forces
The attractive forces between an instantaneous dipole and an induced dipole are called London dispersion forces after the physicist Fritz London.
These forces are stronger for more polarizable species.
Chemistry 120
Intermolecular Forces
Some molecules have a permanent dipole because of differences in electronegativities among the atoms.
Such molecules experience dipole-dipole forces.
All molecules experience dispersion forces and induced dipoles, and polar molecules also experience dipole-dipole forces.
Chemistry 120
Intermolecular Forces
Dipole-dipole interactions.
Chemistry 120
Intermolecular Forces
The intermolecular forces that we have seen
London dispersion forces
induced dipole interactions
dipole-dipole interactions
have a strong effect on the boiling points of liquids, along with the molecular weight of a compound, and hydrogen bonding.
Chemistry 120
Intermolecular Forces
(a) CS2
(b) CH3OH
(c) CH3CH2OH
(d) H2O
(e) C6H5NH2
NH2
Chemistry 120
Intermolecular Forces
Hydrogen bonding is an additional type of bonding interaction that requires a hydrogen atom on one molecule and a source of electron density on another molecule, usually a lone pair.
Hydrogen bonding can be intramolecular as well as intermolecular.
Chemistry 120
Intermolecular Forces
Chemistry 120
Intermolecular Forces
Chemistry 120
Intermolecular Forces
Chemistry 120
Intermolecular Forces
Boiling points of covalent hydrides
Chemistry 120
Intermolecular Forces
Boiling points of covalent hydrides
Chemistry 120
Intermolecular Forces
The second-row hydrides NH3, H2O, and HF exhibit much higher boiling points that would be expected based on their molecular weights. Strong hydrogen bonding between the molecules is responsible for the large liquid phase range of these compounds.
CH4 has a low boiling point because it has no lone pairs to form strong hydrogen bonds.
Chemistry 120
Intermolecular Forces
Hydrogen bonding is crucial for the double-helical structure of DNA.
An understanding of hydrogen bonding between base pairs made the structural solution possible for James Watson and Francis Crick.
Chemistry 120
Intermolecular Forces
DNA base pairs hydrogen bond between
G-C and
A-T
Chemistry 120
Structure and Bonding
bonds are in general stronger than bonds and can be formed from either s or p orbitals:
bonds have no nodal planes along the line containing the two nuclei.
Chemistry 120
Structure and Bonding
The * antibonding orbital has one nodal plane between the two nuclei
Chemistry 120
Structure and Bonding bonds have one nodal plane that contains both nuclei.
The * antibonding orbital also has one nodal plane between the nuclei.
Chemistry 120
Hybridization Review
Recall:
sp3 hybridization 4 bonds
sp2 hybridization 3 bonds, 1 bond
sp hybridization 2 bonds, 2 bonds H
CH H
HC C CC HHH
HHH
sp3 sp2 sp
Chemistry 120
Hybridization Review
H
C
OHHH
H
C C
H
HH
H OH
methanol ethanol
H
OH
water
Chemistry 120
Hybridization Review
H
C
OHHH
H
C C
H
HH
H OH
methanol ethanol
H
OH
water
sp3
Chemistry 120
Hybridization Review
H
C
OHHH
H
C C
H
HH
H OH
methanol ethanol
H
OH
water
sp3 sp3 sp3
Chemistry 120
Hybridization Review
H
C
OHHH
H
C C
H
HH
H OH
methanol ethanol
H
OH
water
sp3 sp3 sp3 sp3
Chemistry 120
Hybridization Review
S C S
carbon disulfide
NH2
aniline
Chemistry 120
Hybridization Review
S C S
carbon disulfide
NH2
aniline
sp
Chemistry 120
Hybridization Review
S C S
carbon disulfide
NH2
aniline
sp2
sp2sp
Chemistry 120
Hybridization Review
S C S
carbon disulfide
NH2
aniline
sp2
sp2
sp3
sp
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