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Lecture 32 : The Hckel Method The material in this lecture covers the following in Atkins. 14.

0 The Hckel approximation (a)The secular determinant (b) Ethene and frontier orbitals (c) Butadiene and p-electron binding energy (d) benzene and aromatic stability

Lecture on-line Huckel Theory (PowerPoint) Huckel Theory (PDF) Handout for this lecture

The Hckel method


The Hckel approximation can be used for conjugated molecules in which there is an alternation of single and double bonds along a chain
One example is the conjugated - systems

Conjugated systems

We shall also use it for the - bond in ethylene

C2H4

Butadiene

Cyclo-Butadiene
allyl cation

Benzene

Molecular orbital theory This leads to the In molecular orbital set of homogeneous theory we write our equations : orbitals as linear combinations of atomic k=n orbitals : Ck Hik WSik = 0 i= n k=1 k (1) = Cii (1)
i= 1

We next require that the corresponding orbital energies

k (1)H k dv W(C1, C2 ,..Cn ) = k (1) k (1)dv Hik WSik = 0 i = 1, 2,...,n; k = 1, 2,...,n be optimal with respect to {C1, C2 ,..Cn } In order to obtain W = 0; i = 1,..,n or : non - trivial solutions Ci

i = 1, 2,...,n. For which the secular determinant must be zero

The Hckel method


We are going to use as our atomic orbitals a single p function on each carbon atom.

Conjugated systems

For ethylene we have two p orbitals

pA

pB

For butadiene we have four p orbitals


The p orbital is the p - function perpendicular to the molecular plane

pA

pB

pC

pD

The Hckel method Ethylene For ethylene we have Non - trivial solutions two p orbitals are only possible if the secular determinant is zero
H11 E H12 - ES12 =0 H21 - ES21 H11 E

pA

pB

For ethylene we can use linear variation theory to obtain a set of linear homogeneous equations
k=n k=1

Each of the two roots W = Ei i = 1, 2 can be substituted into the set of linear equations to obtain orbital coefficients
k=n i= k k Ci p k=1

Ck Hik WSik = 0

k = 1, 2 ; i = 1, 2

i = 1, 2 and n = 1, 2

The Hckel method


For butadiene we have four p orbitals

Butadiene

pA

pB

pC

pD

For butadiene we can use linear variation theory to obtain a set of linear homogeneous equations
k=n

k=1

Ck Hik WSik = 0

i = 1, 4 and n = 1, 4

The Hckel method


Non - trivial solutions are only possible if the secular determinant is zero
H11 E H21 - ES21 H31 - ES31 H41 - ES41

Butadiene

H12 - ES12 H13 - ES13 H14 - ES14 H22 E H23 - ES23 H24 - ES24 =0 H32 - ES32 H33 E H34 - ES34 H42 - ES42 H43 - ES43 H44 E
k=n i= k k Ci p k=1

Each of the two roots W = Ei i = 1, 4 can be substituted into the set of linear equations to obtain orbital coefficients

k = 1, 4 ; i = 1, 4

The Hckel method


The Hckel approximation 1. all overlaps are set to zero S ij = 0

H11 E H12 - ES12 =0 H21 - ES21 H11 E


H11 E H21 - ES21 H31 - ES31 H41 - ES41

H11 E H12 =0 H21 H11 E

H12 - ES12 H13 - ES13 H14 - ES14 H22 E H23 - ES23 H24 - ES24 =0 H32 - ES32 H33 E H34 - ES34 H42 - ES42 H43 - ES43 H44 E

H11 E H21 H31 H41

H12 H22 E H32 H42

H13 H23 H33 E H43

H14 H24 =0 H34 H44

The Hckel method The Hckel approximation 1. All overlaps are set to zero S ij = 0
2. All diagonal terms are set equal to Coulomb integral

H11 E H12 =0 H21 H11 E H11 E H21 H31 H41 E H21 H31 H41 H12 H22 E H32 H42 H12 E H32 H42

E H21 H13 H23 H33 E H43 H13 H23 E H43

H12 =0 E H14 H24 =0 H34 H44 H14 H24 =0 H34 -E

The Hckel method The Hckel approximation 2 1. All overlaps are set to zero S ij = 0 1 3 2. All diagonal terms are set equal to Coulomb integral 3. All resonance integrals between non - neighbours are set to zero
E H21 H12 =0 E

E H21 H13 H23 E H43

H12 =0 E H14 H24 =0 H34 -E

E H21 H31 H41

H12 E H32 H42

E H21 0 0

H12 E H32 0

0 H23 E H43

H34 = 0 -E

0 0

The Hckel method The Hckel approximation 2 1. All overlaps are set to zero S ij = 0 1 3 2. All diagonal terms are set equal to Coulomb integral 3. All resonance integrals between non - neighbours are set to zero 4. All remaining resonance integrals are set to
E H12 E =0 =0 H21 E E H12 0 0 E H21 H23 0 E 0 H32 H34 = 0 E 0 0 H43 -E E 0 0 E 0 =0 0 E 0 0 -E

The Hckel method The Hckel approximation 1. All overlaps are set to zero S ij = 0

2 1 3

2. All diagonal terms are set equal to Coulomb integral 3. All resonance integrals between non - neighbours are set to zero 4. All remaining resonance integrals are set to E =0 E

E 0 0

E 0

0 E

0 0 =0 -E

The Hckel method Solutions for ethylene


E = ( E)2 2 = 0 E

k=n

k=1

Ck Hik WSik = 0

i = 1, 2 and n = 1, 2
k=n i= k Ci pk k=1

( E)2 = 2;( E) =
E1 = + ( and negative) E2 = ( and negative)

k = 1, 2 ; i = 1, 2

1 1 1 2 p + p 2 = 2 2

1 1 1 2 1 = p + p 2 2

The Hckel method Solutions for butadiene E 0 0 E 0 = E 0 -E 0 0 E 0 0 ( E ) E 0 E = 0 E 0 E


2 E ( E )

( E) E 0 ( E )

2 E

20 + = E 0 ( E )

4 4 ( E)2 2 ( E)2 2 ( E)2 2 + ( E )

( E)4 3( E)2 2 + 4 = 0

The Hckel method Solutions for butadiene


( E)4 3( E)2 2 + 4 = 0
Dividing by 2 : ( E ) 4 4 ( - E)2 2 3 ( E )2 2 +1= 0

Introducing : x =

x 2 3x + 1 = 0 x = 2.62 ; x = 0.38

Thus E = 1.62 and 0.62

The Hckel method Solutions for butadiene

k=n

k=1

Ck Hik WSik = 0

i = 1, 4 and n = 1, 4
k=n i= k k Ci p k=1

k = 1, 4 ; i = 1, 4
The Hckel molecular orbital energy levels of butadiene and the top view of the corresponding orbitals. The four p electrons (one supplied by each C) occupy the two lower orbitals. Note that the orbitals are delocalized.

The Hckel method Solutions for butadiene


1

2 3

0.372p1 0.602p2 + 0.602p3 0.372p4


2 1 3 4

0.602pp1 0.3722 0.372p3 + 0.602p4


2 1 3 4

0.602pp1 0.3722 + 0.372p3 + 0.602p4


2 1 3 4

0.372p1 + 0.602p2 + 0.602p3 + 0.372p4

The Hckel method

Solutions for butadiene


Same nodal structure

Comparison between PIB and Huckel treatment of butadiene


Huckel .62

FMO

E3 =

9h2 8mL2

+.62
4h E2 = , 8mL2
2

+1.62

h E1 = 2, 8mL

The Hckel method


Butadiene .62

Solutions for butadiene

We can write butadiene as two localized - bonds


Or two delocalized - bonds
4

+.62

+1.62

E (Bu) 2E (Et) delocalization energy


Ethylene

E (Bu) = 2( + 1.62) + 2( + .62)


= 4 + 4.48

2E (Et) = 4( + ) = 4 + 4
+

Delocalization energy = .48

( 36 kJ mol-1)

The Hckel method

2 1 4

Cyclobutadiene E 0 E 0 E 0

0 =0 -E

0.5p1 0.5p2 + 0.5p3 0.5p4

0.5p1 0.5p2 0.5p3 + 0.5p4

+ 2

0.5p1 + 0.5p2 0.5p3 0.5p4 0.5p1 + 0.5p2 + 0.5p3 + 0.5p4

The Hckel method


2 1 4 3

Cyclobutadiene
2 1 4 3

No delocalization energy
2



+ + 2

The Hckel method

Benzene

The C - C and C - H - orbitals

Benzene

The framework of benzene is formed by the overlap of Csp2 hybrids, which fit without strain into a hexagonal arrangement.

The Hckel method

Benzene

E 0 0

E 0 0 0 0

0 E 0 0

0 0 E

0 -E 0

0 0 -E =0

E = 2; ;

k=n

k=1

Ck Hik WSik = 0

k=n i= k k Ci p k=1

i = 1, 6 and n = 1, 6

k = 1, 6 ; i = 1, 6

The Hckel method

Benzene
Delocalization energy = 2( + 2) + 4( + ) 6( + ) = 2
150 kJ mol-1

+ + 2

What you should learn from this lecture

1. Be able to construct the secular determinant for a conjugated - system within the Huckel approximation
2. Be able to calculate orbital energies for simple systems
3. You will not be asked to find the molecular orbitals. However, you should be able to discuss provided orbitals in terms of bonding and anti - bonding interactions

The Hckel method


allyl cation
2 3

The allyl system

E 0 E 0 E

= 0

1.42 0.5p1 0.707p2 + 0.5p3

0.707p1 0.707p3

+ 1.42

0.5p1 + 0.707p2 + 0.5p3