Honors Organic Chemistry I

Lecture Two:
Molecular Geometry
Molecular Orbitals
So far:
Chemical Bonding and Structure
Why do bonds form?
Bonding models
Lewis structures
VSEPR
Molecular orbitals
Valence bond model (& hybridization)
Drawing Lewis Structures
Simple Lewis structures
Multiple bonds
Formal charges
Resonance structures
Problems with Lewis structures
Continuing:
Chemical Bonding and Structure
VSEPR and bond angles
Polar bonds, polar molecules, and
dipole moments
Electronegativity and polarity
Polarity and geometry
Dipoles and properties
Functional groups

Molecular orbitals
Orbital interaction diagrams
Electrons and wave functions
Understanding MOs
Applications
Molecular Geometry
From 2-D Lewis structures to 3-D
molecular structures
Here are three bonding models that
incorporate three-dimensionality:
Valence Shell Electron Pair Repulsion
Molecular Orbital Theory
The Valence Bond Model (with hybridization)
 Valence Shell Electron Pair
Repulsion (VSEPR)
Predominantly empirical
(closer to a concept than a theory)

Electron pair repulsion (mutual repulsion of

the electron pairs in the valence shell of the same atom)

Drives molecular geometry (which is

assumed to have adjusted so that the distance
between electron pairs is maximized).

So what are the three dimensional consequences?

VSEPR
2 pairs of electrons: linear geometry
(180 bond angles)
3 pairs of electrons: trigonal planar (120
bond angles)
4 pairs of electrons: tetrahedral (109.5
bond angles)
Note: Terms used to describe the molecular geometry of an
atom, such as tetrahedral, are based on the bonding angles
that are defined by the nucleus of that atom and those of the
atoms bonded to it. These terms do not include or describe the
arrangement of the non-bonded electrons of the central atom
(although the angles of those electron orbitals can usually be
deduced, as we shall see later).
VSEPR
4 pairs of electrons: tetrahedral ?
4 bonding electron pairs: tetrahedral (109.5
bond angles)
3 bonding, 1 nonbonding pair: trigonal
pyramid (<109.5 bond angles)
2 bonding, 2 nonbonding: bent (< trigonal)
Are atoms with 4 unshared electron pairs
tetrahedral, or not?
Nonbonding pairs apparently require more
space than bonding pairs ...therefore the
angle between bonded atoms tends to be
compressed if lone pairs are also present.
Problem 2-1
Draw Lewis structures and use VSEPR to
predict and draw three-dimensional
molecular structures for the following:
a) PCl3
b) BF3
c) F3B-NH3
d) H2Se
Polar and Nonpolar Covalent Bonds
Until now, we have been working with two
extreme models of bonding:
Covalent bonds:
CC C C
implies

equal sharing of electrons But of course

the world
Ionic bonds: rarely
operates at
Na+ Cl the extremes.
complete transfer of electrons
Polar and Nonpolar Covalent Bonds
are the result when the sharing of
electrons is equal:
C C

but... Polar Covalent Bonds

arise when the sharing of electrons is
not equal:

C X
 Polar Covalent Bonds
The unequal sharing of electrons gives rise to
bond dipoles.
But why is there unequal sharing?
Different atoms have different electronegativities.
Electronegativity is a measure of the ability of an
atoms nucleus to attract the electrons in a
covalent bond.
Lets look at the example of
hydrogen chloride gas:
H Cl
 Polar Covalent Bonds
Cl is more electronegative than H.
Result: an unequal sharing of electrons.
The bonding electrons are skewed towards Cl.

H Cl
Area of lower Area of higher
electron electron
density density

Other types of +
representations: HCl or HCl
 Polarity and Electronegativity
So...bond polarities arise from unequal
sharing of electron density, and unequal
sharing can be attributed to the differences
in the electronegativities of the atoms.
Remember the trends in the
Periodic Table:
Electronegativity
Electronegativity

increases
increases
 Polarity and Electronegativity

The most widely used

electronegativity scale is one
devised by Linus Pauling
Polarity and Electronegativity

2.20
Here are some useful values:
2.04 2.55 3.04 3.44 3.98

3.16

2.96

2.66

For more values see table in your text.

(Table 1.1, p.9)
 Molecular Polarity
...arises from the net sum of bond polarities.
Find the geometric sum of the individual bond
polarities.
Unless the bond polarities cancel the
molecule is polar.
Example:
Cl Cl The bond
dipoles cancel.
ClCCl C Dipole
Cl
Cl Moment
Cl
carbon tetrachloride Cl =0
Why is carbon tetrachloride tetrahedral?
 Molecular Polarity
Find the geometric sum of the individual bond
polarities.
Unless the bond polarities cancel the
molecule is polar.
Example: The bond
Cl Cl dipoles do not
cancel.
HCH
C Dipole
H Moment
Cl
dichloromethane Cl 0
H
Is dichloromethane tetrahedral?
Problem 2-2
Determine whether the following
molecules have a dipole moment
a. BF3
b. CH2O
c. C2H6
 Dipole magnitudes can tell us a lot about
molecular structure and geometry.
Compound (Debye)
-
:C
+
O : 0.112 D Why is the dipole of CO so
H much smaller than that of
C O 2.33 D formaldehyde?
H
CO2 0.0 D SO2 has a dipole, why
doesnt CO2?
SO2 1.63 D What can we conclude
about the geometry of
SO 1.55 D SO2 by comparing its
dipole with that of SO?
 Polarity is a major determinant of
how organic molecules interact
Molecular dipoles align in an antiparallel
manner that maximizes attraction.
This alignment - + Dipole-dipole
makes cohesion attractions are
stronger in crystals also dominant
+ -
(increases the m.p.) forces in the
and leads to
- + formation of
highly associated solutions.
(high b.p.) liquids.
See Loudons section 2.6C.
 Polarity is a major determinant of
how organic molecules interact
You may recall first hearing about such
types of interactions as intermolecular
forces (IMFs). You will encounter many more
examples of these in the laboratory class.

More often than not, they are attractive in

nature (IMAFs).
They represent physical aspects of the
influence of molecular functional groups.
So what are organic functional groups?
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 Organic functional groups
involve either:
heteroatoms
(Heteroatoms are atoms of elements other than
carbon or hydrogen that appear in the structure.)
or multiple bonds.
(Multiple bonds involve two or three bonds between
the same pair of atoms within an organic structure.)
Functional groups are normally regarded as potential
sites of chemical reactivity in organic molecules.
There is a table of functional groups inside the front
cover of Louden. Eventually, you will learn them all.
 Functional Group Reactivity
...may involve physical or chemical reactions.
We studied three molecules with functional groups
during the first lecture (although only one is organic):

HC CH FBF

H H F

H
...and we watched two of them react.
NH

What do you think gives rise to

functional group reactivity?
H
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 Back to Models of Bonding
The effects of bonding and molecular geometry
on molecular behavior are becoming evident.
These factors lie at the heart of how organic
chemists explain molecular properties...in other
words, those interactions that you observe in the
laboratory....or in the world around you.
If we accept that a molecules structure and its
properties are related, or even if we just want to
test whether that is so, we need to consider
some more sophisticated models of bonding.

We will start with the LCAO-MO model.

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 The LCAO-MO Model
The LCAO-MO model constructs molecular
orbitals (bonds) from appropriate atomic
orbitals of the atoms that are bonding.
Suitable orbitals from each atom involved are
added to, or subtracted from, each other. This
process generates a set of molecular orbitals.
The designation, LCAO-MO comes from:
Linear Combination of Atomic
Orbital - Molecular Orbital.
 The LCAO-MO Model
The orbitals generated by the LCAO-MO
model are still approximations of the
actual orbitals, but they do give very
good pictures of how the electrons are
distributed across the bonded atoms.
They also allow chemists to make good
estimates of relative bond energies.
Lets pick up where we left off in our earlier
discussion of why and how atoms bond.
 Review: Picturing Bond Formation

Consider two hydrogen atoms joining to form a molecule:

The two electron clouds merged.

What happened to the electron energies?

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 Bonding Energy Diagram
You recall this way of depicting bond formation...
(sometimes called a Morse curve)

0
E

and you remember what this

represents...
and this point.

Internuclear distance
Another way to show this is with an Orbital Interaction Diagram.
An Orbital Interaction Diagram of the Hydrogen Molecule
When a molecule of H2 is
formed by bringing together What is this gap?
two H atoms, the two atomic Why are the two lobes
interact (recombine) to form different colors?
two molecular orbitals. This
can be shown graphically. Antibonding
Energy Orbital 2*

---- - - Ave. energy of a non-bonded H electron - - ----

The total energy of the electrons

when they occupy one of the
Bonding
recombined orbitals is lower Orbital 1
than when they were in the
isolated atomic orbitals. This picture looks
The energy of any electrons that familiar.
occupy the second molecular
orbital will be relatively higher.
An Orbital Interaction Diagram of the Hydrogen Molecule

Antibonding
Energy Orbital 2*

---- - - Ave. energy of a non-bonded H electron - - ----

Note that the Bonding

destabilization Orbital 1
of *2 ... is actually The significance of
greater than the this difference will
stabilization of 1. become clear later.
 Calculating Molecular Orbitals
Just as with atomic orbitals, the energies of
the molecular orbitals are calculated using
Schrdingers equation: E = H
Schrdingers equation describes an electron
orbital by using a wave function, . That is, the
electron is treated as a wave, not as a particle.
Just as light can have properties of a particle, an electron
can have the behavior of a wave.
We can predict the energy, E, of an electron in a particular
orbital by multiplying the wave function of that orbital, ,
by the energy operator, H. (In this kind of equation the operator,
H, functions in a manner similar to a coefficient.)
 Calculating Molecular Orbitals
How do we apply the LCAO-MO approach to
Schrdingers equation?
E = H
The wave function, , is actually a set of wave
equations, 1, 2, etc. In other words, there are
several different solutions to the equation for a
given bond. Each solution corresponds to a
different energy level. Using LCAO-MO, each
energy level is calculated by adding or subtracting
(combining) a fraction of each of the atomic
orbitals (n) used to form the new bond(s).
Lets see an example.
 AOs to MOs
The H2 molecule has two MOs, 1 and *2.
They were generated by mixing two AOs,
1 and 2.
Remember, a belongs to the molecule, but the s belong
to individual atoms; in this case to H1 and H2.
1 = 11 + 22 The s are fractional
and coefficients.
* Indicates an
*2 = 31 - 42 antibonding orbital.

MO calculations may involve different combinations

of many AOs, but one relationship is always true:
# MOs produced = # AOs used.
 AOs to MOs
# MOs produced = # AOs used.

To put it simply: Each molecular orbital uses

some fraction of each atomic orbital.

The sum of all the fractional parts used to

construct a single MO is equivalent to the
space available in a single AO.

Each AO contributes to the set of MOs, and its

total contribution to the set is its entire space.
Standing Waves, Quantum Levels and Nodes
Schrdingers equation treats an electron near a nucleus
by using a wave functionthat is, as if it were a wave.

Lets think about waves; specifically about standing

waves, such as a vibrating strings. Strings can
only vibrate at fixed frequencies that are multiples
of their fundamental frequencies. (The wavelength of
the fundamental frequency is exactly twice the length of the
string.)

The fixed vibrational frequencies are

quantized energy levels.
 Standing Waves and Quantum Levels
The first two quantum levels of a vibrating
string are:
Next
energy 2 one node
level

Lowest
energy 1 no nodes
level

How do these apply to the orbitals

of a hydrogen molecule?
Wave Functions to Orbitals

This is the node of

*2 the molecular orbital
The wave function
(*) has a different
sign (+ or -) in each
lobe. The two lobes
are out of phase
because the atomic
1 orbitals are out of
phase.
 Review

*2

H ---- - - - - - - - - - - - ---- H

1
 What if we used two He atoms?

He ---- - - - - - - - - - - - ---- He

Draw the distribution of the

electrons and explain the result.
 Minsky on Understanding
If you understand something in only
one way, then you scarcely understand it
at allbecause when you get stuck,
youll have nowhere to go. But if you
represent something in several ways,
then when you get frustrated enough,
you can switch among different points of
view, until you find one that works for
you! Marvin Minsky
The Emotion Machine
Commonsense thinking,
Artificial Intelligence and the
Future of the Human Mind
Simon and Schuster, NY 2006
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