Huckel

The Hückel method: Applications to
allyl, butadiene and cyclobutadiene
Albeiro Restrepo
Grupo de Quı́mica–Fı́sica Teórica θ–φ τ

Instituto de Quı́mica
Universidad de Antioquia
May 31, 2013
Albeiro Restrepo (UdeA) Hückel method May 31, 2013 1 / 50

Outline
1 Theoretical background
Molecular Hamiltonian
Variational theorem
Linear combination of atomic orbitals
Secular determinant
2 Hückel method
Generalities
Basis set
Overlap integrals
Energy integrals
The working secular determinant
The working secular determinant
3 Specific cases
Allyl system
Butadiene
Cyclobutadiene
Theoretical background Molecular Hamiltonian
We derived in class the molecular Hamiltonian under the Born–Oppenheimer

approximation (BOA).


approximation (BOA). It comprises the kinetic energy of the electrons (Te ),
the potential energy for the interactions between electrons (Vee ), and the
potential energy for the interactions between nuclei and electrons (VeN ):


H = Te + Vee + VNN


H = Te + Vee + VNN
n n n n N
1 X 2 XX 1 X X ZA
H=− ∇i + −
2 rij riA
i=1 i=1 j>i i=1 A=1

Schrödinger’s equation with this Hamiltonian
H |Ψi = E |Ψi
is a second order differential equation in partial derivatives with non–separable

variables.

H |Ψi = E |Ψi

variables. This sort of equations have no known analytical solutions.

H |Ψi = E |Ψi

variables. This sort of equations have no known analytical solutions. The
offending terms are the inverse distances:
1 1
=q
rij
(xi − xj )2 + (yi − yj )2 + (zi − zj )2

Theoretical background Variational theorem
Variational theorem
No analytical solutions? No problem!

Variational theorem
No analytical solutions? No problem! we invent them.

Variational theorem
The variational theorem (we derived it in class) tells us that for whatever
solution we come up with, the energy associated will be larger than the
ground state energy
Et ≥ ε0

Variational theorem
ground state energy
Et ≥ ε0
This provides us with a recipe to obtain the best possible solution among a
family of trial functions:

Variational theorem
ground state energy
Et ≥ ε0
This provides us with a recipe to obtain the best possible solution among a
family of trial functions: Write down trial functions with parameters ci , and
then minimize the energy with respect to those parameters:
∂E
= 0, ∀i
∂ci

Theoretical background LCAO
Linear Combination of Atomic Orbitals (LCAO)

For the molecular case, construct molecular orbitals |ψµ i from linear com-
binations of atomic orbitals |φi i 1
1
Please notice that as mentioned in class, molecular orbitals are one-particle
functions while the molecular wavefunction is a many–particle wavefunction!

n
X
|ψµ i = cµi |φi i
i=1
1

n
X
i=1
If there are n basis functions (AOs), then there are a total of n2 expansion
coefficients, n for each molecular orbital.
1

n
X
i=1
If there are n basis functions (AOs), then there are a total of n2 expansion
coefficients, n for each molecular orbital. I will now drop the µ subscript
with the understanding that for each molecular orbital, there will be a cor-
responding linear combination:
n
X
|ψi = ci |φi i
i=1
1
LCAO
In class, we found out that for each molecular orbital, minimizing the energy
with respect to ck , the expansion coefficients, leads to a series of n linear
homogeneous equations with constant coefficients:
c1 (H11 − ES11 ) + c2 (H12 − ES12 ) + · · · + cn (H1n − ES1n ) = 0

.. .. .. ..
. . . .
c1 (Hn1 − ESn1 ) + c2 (Hn2 − ESn2 ) + · · · + cn (Hnn − ESnn ) = 0

LCAO
In class, we found out that for each molecular orbital, minimizing the energy
with respect to ck , the expansion coefficients, leads to a series of n linear
homogeneous equations with constant coefficients:

.. .. .. ..
. . . .
c1 (Hn1 − ESn1 ) + c2 (Hn2 − ESn2 ) + · · · + cn (Hnn − ESnn ) = 0
Which can be compactly written as

n
X
ci (Hki − ESki ) = 0, ∀k
i=1

Theoretical background Secular determinant
Secular determinant
Our goal is to find the set of expansion coefficients {ci }, that minimize the
energies of the molecular orbitals.

Secular determinant
energies of the molecular orbitals. As discussed in class, there are non–
trivial solutions for a system of homogeneous linear equations when the
determinant of the coefficients vanishes:

H11 − ES11 H12 − ES12 · · · H1n − ES1n

H21 − ES21 H22 − ES22 · · · H2n − ES2n
= 0

.. .. .. ..

. . . .

Hn1 − ESn1 Hn2 − ESn2 · · · Hnn − ESnn

Secular determinant

H11 − ES11 H12 − ES12 · · · H1n − ES1n

H21 − ES21 H22 − ES22 · · · H2n − ES2n
= 0

.. .. .. ..

. . . .

Hij = hφi |H| φj i Sij = hφi |φj i

Secular determinant

H11 − ES11 H12 − ES12 · · · H1n − ES1n

H21 − ES21 H22 − ES22 · · · H2n − ES2n
= 0

.. .. .. ..

. . . .

Hij = hφi |H| φj i Sij = hφi |φj i
Since H and S are Hermitean, this determinant has n real roots, corre-
sponding to the energies of the n molecular orbitals.

Hückel method Generalities
Hückel method generalities
In its original version, the method was developed to treat


Conjugated hydrocarbons (alternating double/single bonds)


Planar systems


Planar systems
Linear or cyclic


Planar systems
Linear or cyclic
Successful applications


Planar systems
Linear or cyclic
Color theory


Planar systems
Linear or cyclic
Color theory
Aromaticity


Planar systems
Linear or cyclic
Color theory
Aromaticity
Conducting polymers


Planar systems
Linear or cyclic
Color theory
Aromaticity
Conducting polymers
···

Hückel method Basis set
Hückel method: basis set

A crucial step when applying the variational method to any problem, is to
devise a basis set that spans the vector space (the solution space) of the
operator.


operator.
Since the method treats conjugated hydrocarbons, an appropriate choice is

a set of pz orbitals located on each carbon atom.


operator.
Since the method treats conjugated hydrocarbons, an appropriate choice is

a set of pz orbitals located on each carbon atom. An even more convenient
choice, is a set of pz orbitals from the methyl radical, in which the carbon
atom has the proper geometry and hybridization:

The chosen basis set consists in a set of pz orbitals
{|ψ2pz i } ≡ {|φi i }
each carbon atom, has one such orbital, containing one electron

The chosen basis set consists in a set of pz orbitals
{|ψ2pz i } ≡ {|φi i }
each carbon atom, has one such orbital, containing one electron
Bonus alert: The energy of this orbital is experimentally accessible: Koop-

manns’ theorem says that it is the negative of the ionization energy of the
methyl radical
hψ2pz |H| ψ2pz i = ε2pz = hφi |H| φi i = Hii = εi = −Ip (CH3 ·)

Hückel method Overlap integrals
Hückel method: overlap integrals
The secular determinant contains the elements of the overlap matrix
Sij = hφi |φj i

Sij = hφi |φj i
Hückel method neglects overlap for orbitals that do not belong to the same
carbon atom:

1 if |φi i , |φj i ∈ same atom
Sij =
0 otherwise

Sij = hφi |φj i
Hückel method neglects overlap for orbitals that do not belong to the same
carbon atom:

1 if |φi i , |φj i ∈ same atom
Sij =
0 otherwise
Notice that this is a severe simplification since orbital overlap is crucial for
bonding.

Hückel method Energy integrals
Hückel method: energy integrals
We already stated that the Hii terms are known, let’s call them α:
hψ2pz |H| ψ2pz i = ε2pz = hφi |H| φi i = Hii = εi = −Ip (CH3 ·) = α

The energy associated with the interaction between electrons in orbitals i

and j in adjacent carbon atoms is given by Hij , the resonant integral:
Hij = hφi |H| φj i = β

The energy associated with the interaction between electrons in orbitals i

and j in adjacent carbon atoms is given by Hij , the resonant integral:
Hij = hφi |H| φj i = β
What does this interaction energy represent?

Consider two approaching pz orbitals, eventually leading to the formation

of a π bond


Consider two approaching pz orbitals, eventually leading to the formation
of a π bond
=⇒

Now consider the energy of two parallel interacting pz orbitals, and the
energy of two perpendicular non interacting pz orbitals (if the orbitals are
perpendicular Hij vanishes)


E = Eπ E = 2α

The difference in energy between these two systems is the interaction energy.

Let’s call this interaction energy 2β (as you see, β can also be experimentally
measured!):

measured!):
2β = Eπ − 2α =⇒ Eπ = 2α + 2β

measured!):
2β = Eπ − 2α =⇒ Eπ = 2α + 2β
In this treatment, both α and β are negative

measured!):
2β = Eπ − 2α =⇒ Eπ = 2α + 2β
Hückel’s model neglects interaction between electrons not belonging to

neighboring atoms, thus, in this model, energy integrals are set to

measured!):
2β = Eπ − 2α =⇒ Eπ = 2α + 2β


 α if |φi i , |φj i ∈ same atom
Hij =


measured!):
2β = Eπ − 2α =⇒ Eπ = 2α + 2β


Hij = β if |φi i , |φj i ∈ neighbor atoms


measured!):
2β = Eπ − 2α =⇒ Eπ = 2α + 2β


Hij = β if |φi i , |φj i ∈ neighbor atoms
0 otherwise


Hückel method The working secular determinant
Hückel method: working secular determinant
Let’s analyze the effect of Hückel’s approximations in the secular determi-

nant for linear conjugated hydrocarbons



H11 − ES11 H12 − ES12 · · · H1n − ES1n

H21 − ES21 H22 − ES22 · · · H2n − ES2n

.. .. .. ..

. . . .




H11 − ES11 H12 − ES12 · · · H1n − ES1n

H21 − ES21 H22 − ES22 · · · H2n − ES2n

.. .. .. ..

. . . .

First, eliminate all vanishing overlap elements and set Sii = 1:



H11 − ES11 H12 − ES12 · · · H1n − ES1n

H21 − ES21 H22 − ES22 · · · H2n − ES2n

.. .. .. ..

. . . .

First, eliminate all vanishing overlap elements and set Sii = 1:

H11 − E H12 H13 · · · H1n

H21
H 22 −E H23 · · · H2n
.. .. .. .. ..

. . . . .

Hn1 Hn2 Hn3 · · · Hnn − E

Now, set Hii = α:

Now, set Hii = α:

α−E H12 H13 · · · H1n−1 H1n

H21
α−E H23 · · · H2n−1 H2n

.. .. .. .. .. ..

. . . . . .

Hn1 Hn2 Hn3 · · · Hnn−1 α − E

Now, set Hii = α:

α−E H12 H13 · · · H1n−1 H1n

H21
α−E H23 · · · H2n−1 H2n

.. .. .. .. .. ..

. . . . . .

Hn1 Hn2 Hn3 · · · Hnn−1 α − E
Next, set Hij = β for neighboring atoms:

Now, set Hii = α:

α−E H12 H13 · · · H1n−1 H1n

H21
α−E H23 · · · H2n−1 H2n

.. .. .. .. .. ..

. . . . . .

Hn1 Hn2 Hn3 · · · Hnn−1 α − E
Next, set Hij = β for neighboring atoms:

α−E β H13 · · · H1n−1 H1n

β
α − E β · · · H2n−1 H2n

.. .. .. .. .. ..

. . . . . .

Hn1 Hn2 Hn3 · · · β α−E

Finally, set the remaining Hij = 0:


α−E β 0 ··· 0 0

β
α−E β ··· 0 0

.. .. .. .. .. ..

. . . . . .

0 0 0 ··· β α − E


α−E β 0 ··· 0 0

β
α−E β ··· 0 0

.. .. .. .. .. ..

. . . . . .

0 0 0 ··· β α − E
As stated earlier, the energies for the molecular orbitals are the roots of the
secular determinant obtained by solving

α−E β 0 ··· 0 0

β α − E β ··· 0 0
= 0

.. .. .. .. .. ..

. . . . . .

0 0 0 ··· β α − E

Specific cases Allyl system
The Allyl system

The Allyl system

The allyl system can be considered as existing in cationic (2 π electrons),
neutral (3 π electrons) and anionic (4 π electrons) forms

The Allyl system

The allyl system can be considered as existing in cationic (2 π electrons),
neutral (3 π electrons) and anionic (4 π electrons) forms

The Allyl system

The secular equation for the π system takes the form

The Allyl system


α−E β 0

β
α−E β = 0
0 β α−E

The Allyl system


α−E β 0

β
α−E β = 0
0 β α−E
which leads to

α−E β β β
(α − E ) − β +0 = 0
β α−E 0 α−E

The Allyl system


α−E β 0

β
α−E β = 0
0 β α−E
which leads to

α−E β β β
(α − E ) − β +0 = 0
β α−E 0 α−E
(α − E ) (α − E )2 − β 2 − β [β(α − E )] = 0


The Allyl system


α−E β 0

β
α−E β = 0
0 β α−E
which leads to

α−E β β β
(α − E ) − β +0 = 0
β α−E 0 α−E
(α − E ) (α − E )2 − β 2 − β [β(α − E )] = 0

(α − E )3 − 2β 2 (α − E )

The Allyl system


α−E β 0

β
α−E β = 0
0 β α−E
which leads to

α−E β β β
(α − E ) − β +0 = 0
β α−E 0 α−E
(α − E ) (α − E )2 − β 2 − β [β(α − E )] = 0

(α − E )3 − 2β 2 (α − E ) = (α − E ) (α − E )2 − 2β 2 = 0


The Allyl system
The roots are now easily obtained from

The Allyl system
(α − E ) = 0, (α − E )2 − 2β 2 = 0

The Allyl system
(α − E ) = 0, (α − E )2 − 2β 2 = 0
Therefore,
α = E,

The Allyl system
(α − E ) = 0, (α − E )2 − 2β 2 = 0
Therefore,
√
α = E, (α − E )2 = 2β 2 =⇒ α − E = ± 2β

The Allyl system
(α − E ) = 0, (α − E )2 − 2β 2 = 0
Therefore,
√ √
α = E, (α − E )2 = 2β 2 =⇒ α − E = ± 2β =⇒ E = α ± 2β

The Allyl system
(α − E ) = 0, (α − E )2 − 2β 2 = 0
Therefore,
√ √
α = E, (α − E )2 = 2β 2 =⇒ α − E = ± 2β =⇒ E = α ± 2β
Recall that both α, β < 0, therefore, sorting the energies in increasing order,
we have
√ √
E1 = α + 2β, E2 = α, E3 = α − 2β

The Allyl system: correlation diagram

2p z 2p z

2p z
|ψ 1 > , ε 1 = α + 1.41β

2p z |ψ2 > , ε 2 = α
|ψ 1 > , ε 1 = α + 1.41β

|ψ3 > , ε3 = α − 1.41β
2p z |ψ2 > , ε 2 = α
|ψ 1 > , ε 1 = α + 1.41β

The Allyl cation system (2π electrons): correlation diagram
|ψ3 > , ε3 = α − 1.41β
2p z |ψ2 > , ε 2 = α
|ψ 1 > , ε 1 = α + 1.41β

The Allyl radical system (3π electrons): correlation

diagram
|ψ3 > , ε3 = α − 1.41β
2p z |ψ2 > , ε 2 = α
|ψ 1 > , ε 1 = α + 1.41β

The Allyl anion system (4π electrons): correlation diagram
|ψ3 > , ε3 = α − 1.41β
2p z |ψ2 > , ε 2 = α
|ψ 1 > , ε 1 = α + 1.41β

The Allyl system delocalization energy
How much energy is gained by delocalizing the electrons?

How much energy is gained by delocalizing the electrons?
Ed = EHuckel − Elocalized π system


Allyl cation


Allyl cation, delocalized system: 2 electrons in |ψ1 i , ε1 = α + 1.41β;


localized system: 2 electrons in a π bond:


Ed = 2(α + 1.41β) − 2(α + β)


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β
Allyl radical


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β
Allyl radical, delocalized system: 2 electrons in |ψ1 i , ε1 = α + 1.41β and

one electron in |ψ2 i , ε2 = α;


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

one electron in |ψ2 i , ε2 = α; localized system: 2 electrons in a π bond
and one electron in a 2pz orbital:


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

√
Ed = 2(α + 2β) + α − {2(α + β) + α}


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

√
Ed = 2(α + 2β) + α − {2(α + β) + α} = 0.82β


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

√
Ed = 2(α + 2β) + α − {2(α + β) + α} = 0.82β
Allyl anion


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

√
Ed = 2(α + 2β) + α − {2(α + β) + α} = 0.82β
Allyl anion, delocalized system: 2 electrons in |ψ1 i , ε1 = α + 1.41β and

two electrons in |ψ2 i , ε2 = α;


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

√
Ed = 2(α + 2β) + α − {2(α + β) + α} = 0.82β

two electrons in |ψ2 i , ε2 = α; localized system: 2 electrons in a π bond
and two electrons in a 2pz orbital:


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

√
Ed = 2(α + 2β) + α − {2(α + β) + α} = 0.82β

√
Ed = 2(α + 2β) + 2α − {2(α + β) + 2α}


Ed = 2(α + 1.41β) − 2(α + β) = 0.82β

√
Ed = 2(α + 2β) + α − {2(α + β) + α} = 0.82β

√
Ed = 2(α + 2β) + 2α − {2(α + β) + 2α} = 0.82β

This result is obviously not right: the three systems cannot have the same
delocalization energy!

delocalization energy! Where did we go wrong?

1 Besides all the approximations before and during Hückel’s method,


2 We did not consider orbital relaxation after electrons are added


3 We did not consider geometry relaxation after electrons are added


When we know the limitations of our models, we are better equipped to

understand inconsistent results.


When we know the limitations of our models, we are better equipped to

understand inconsistent results.
How do the molecular orbitals look like?

The Allyl system
In order to find the molecular orbitals we use the system of equations ob-
tained earlier after minimization of the energy with respect to the expansion
coefficients

The Allyl system
coefficients
n
X
i=1

The Allyl system
coefficients
n
X
i=1
c1 (α − E ) + c2 β + c3 × 0 =0

The Allyl system
coefficients
n
X
i=1
c1 (α − E ) + c2 β + c3 × 0 =0
c1 β + c2 (α − E ) + c3 β =0

The Allyl system
coefficients
n
X
i=1
c1 (α − E ) + c2 β + c3 × 0 =0
c1 β + c2 (α − E ) + c3 β =0
c1 × 0 + c2 β + c3 (α − E ) = 0

The Allyl system
coefficients
n
X
i=1
c1 (α − E ) + c2 β + c3 × 0 =0
c1 β + c2 (α − E ) + c3 β =0
c1 × 0 + c2 β + c3 (α − E ) = 0
√
Let’s set the equations for the coefficients associated with E1 = α + 2β,
the lowest energy π MO

The Allyl system
√
c1 α − α + 2β + c2 β + c3 × 0 =0

The Allyl system
√
c1 α − α + 2β + c2 β √ + c3 × 0 =0
c1 β + c2 α − α + 2β + c3 β =0

The Allyl system
√
c1 α − α + 2β + c2 β √ + c3 × 0 =0
c1 β + c2 α − α + 2β + c3 β √ =0
c1 × 0 + c2 β + c3 α − α + 2β =0

The Allyl system
√
c1 α − α + 2β + c2 β √ + c3 × 0 =0
c1 β + c2 α − α + 2β + c3 β √ =0
c1 × 0 + c2 β + c3 α − α + 2β =0
√
−c1 2β + c2√β + c3 × 0 = 0
c1 β + −c2 2β + c3√
β =0
c1 × 0 + c2 β + −c3 2β = 0

The Allyl system
√
c1 α − α + 2β + c2 β √ + c3 × 0 =0
c1 β + c2 α − α + 2β + c3 β √ =0
c1 × 0 + c2 β + c3 α − α + 2β =0
√
−c1 2β + c2√β + c3 × 0 = 0
c1 β + −c2 2β + c3√
β =0
c1 × 0 + c2 β + −c3 2β = 0
The solutions are then
√
c1 , c2 = 2c1 , c3 = c1

The Allyl system
√
c1 α − α + 2β + c2 β √ + c3 × 0 =0
c1 β + c2 α − α + 2β + c3 β √ =0
c1 × 0 + c2 β + c3 α − α + 2β =0
√
−c1 2β + c2√β + c3 × 0 = 0
c1 β + −c2 2β + c3√
β =0
c1 × 0 + c2 β + −c3 2β = 0
The solutions are then
√
c1 , c2 = 2c1 , c3 = c1
To obtain the exact values for the coefficients, let’s use the normalization
condition
The Allyl system
3
X
ci2 = 1
i=1

The Allyl system
3
X √
ci2 = 1 =⇒ c12 + ( 2c1 )2 + c12 = 1
i=1

The Allyl system
3
X √ 1
ci2 = 1 =⇒ c12 + ( 2c1 )2 + c12 = 1 =⇒ c1 =
2
i=1

The Allyl system
3
X √ 1
ci2 = 1 =⇒ c12 + ( 2c1 )2 + c12 = 1 =⇒ c1 =
2
i=1
Therefore, the lowest π MO for the allyl system is found to be

√
1 2 1 √
|ψ1 i = |ψ2pz (1)i + |ψ2pz (2)i + |ψ2pz (3)i , E1 = α + 2β
2 2 2

The Allyl system
3
X √ 1
ci2 = 1 =⇒ c12 + ( 2c1 )2 + c12 = 1 =⇒ c1 =
2
i=1

√
1 2 1 √
2 2 2
The other two π MOs are obtained in the same way

√ √
2 2
|ψ2 i = |ψ2pz (1)i + 0 |ψ2pz (2)i − |ψ2pz (3)i , E2 = α
2 2

The Allyl system
3
X √ 1
ci2 = 1 =⇒ c12 + ( 2c1 )2 + c12 = 1 =⇒ c1 =
2
i=1

√
1 2 1 √
2 2 2
The other two π MOs are obtained in the same way

√ √
2 2
|ψ2 i = |ψ2pz (1)i + 0 |ψ2pz (2)i − |ψ2pz (3)i , E2 = α
2 2
√
1 2 1 √
|ψ3 i = |ψ2pz (1)i − |ψ2pz (2)i + |ψ2pz (3)i , E3 = α − 2β
2 2 2
The Allyl system: molecular orbitals
Orbital shape Energy Occ. Occ. Occ. nodes

cation radical anion
√
|ψ3 i α− 2β 0 0 0 2


√
|ψ3 i α− 2β 0 0 0 2
|ψ2 i α 0 1 2 1


√
|ψ3 i α− 2β 0 0 0 2
|ψ2 i α 0 1 2 1
√
|ψ1 i α+ 2β 2 2 2 0

Specific cases Butadiene
Butadiene
From the point of view of Hückel’s method, the conformation of butadiene
is irrelevant

Butadiene
is irrelevant so, here are the two possible conformations in a localized view

Butadiene
is irrelevant so, here are the two possible conformations in a localized view
And here are the same structures in a delocalized picture

Butadiene

Butadiene

α−E β 0 0

β α−E β 0
=0
0
β α−E β
0 0 β α−E

Butadiene

α−E β 0 0

β α−E β 0
=0
0
β α−E β
0 0 β α−E
which leads to

α−E β 0 β β 0

(α − E ) β α−E β −β 0 α−E
β = 0

0 β α−E 0 β α−E

Butadiene

α−E β 0 0

β α−E β 0
=0
0
β α−E β
0 0 β α−E
which leads to

α−E β 0 β β 0

(α − E ) β α−E β −β 0 α−E
β = 0

0 β α−E 0 β α−E
Keep going, and you eventually reach
(α − E )4 − 3(α − E )2 β 2 + β 4 = 0

Butadiene: correlation diagram

With the obtained energies sorted in increasing order, the correlation dia-
gram looks like this
|ψ > , ε = α − 1.62β
4 4
|ψ > , ε 3 = α − 0.62β
3
2p z
|ψ > , ε = α + 0.62β
2 2
|ψ 1 > , ε 1 = α + 1.62β

Butadiene
Butadiene delocalization energy:

Butadiene
Delocalized system: 2 electrons in |ψ1 i , ε1 = α + 1.62β and two electrons

in |ψ2 i , ε2 = α + 0.62β

Butadiene

in |ψ2 i , ε2 = α + 0.62β
localized system: 4 electrons in two π bonds:

Butadiene

in |ψ2 i , ε2 = α + 0.62β
localized system: 4 electrons in two π bonds:
Ed = 2(α + 1.62β) + 2(α + 0.62β) − 4(α + β) = 0.48β

Butadiene molecular orbitals
The molecular orbitals for butadiene are obtained following the same pro-
cedure as for the allyl system:


|ψ4 i = 0.372 ψ2pz (1)i − 0.602 ψ2pz (2)i + 0.602 ψ2pz (3)i − 0.372 ψ2pz (4)i , E4 = α − 1.62β

|ψ3 i = 0.602 ψ2pz (1)i − 0.372 ψ2pz (2)i − 0.372 ψ2pz (3)i + 0.602 ψ2pz (4)i , E3 = α − 0.62β

|ψ2 i = −0.602 ψ2pz (1)i − 0.372 ψ2pz (2)i + 0.372 ψ2pz (3)i + 0.602 ψ2pz (4)i , E2 = α + 0.62β

|ψ1 i = 0.372 ψ2pz (1)i + 0.602 ψ2pz (2)i + 0.602 ψ2pz (3)i + 0.372 ψ2pz (4)i , E1 = α + 1.62β


|ψ4 i = 0.372 ψ2pz (1)i − 0.602 ψ2pz (2)i + 0.602 ψ2pz (3)i − 0.372 ψ2pz (4)i , E4 = α − 1.62β

|ψ3 i = 0.602 ψ2pz (1)i − 0.372 ψ2pz (2)i − 0.372 ψ2pz (3)i + 0.602 ψ2pz (4)i , E3 = α − 0.62β

|ψ2 i = −0.602 ψ2pz (1)i − 0.372 ψ2pz (2)i + 0.372 ψ2pz (3)i + 0.602 ψ2pz (4)i , E2 = α + 0.62β

|ψ1 i = 0.372 ψ2pz (1)i + 0.602 ψ2pz (2)i + 0.602 ψ2pz (3)i + 0.372 ψ2pz (4)i , E1 = α + 1.62β
|ψ1 i has no nodes, |ψ2 i has 1 node, |ψ3 i has 2 nodes, |ψ4 i has 3 nodes

Molecular orbitals for butadiene
|ψ1 i |ψ2 i
|ψ3 i |ψ4 i

Specific cases Cyclobutadiene
Cyclobutadiene
Here are the localized and delocalized pictures

Cyclobutadiene

Cyclobutadiene

α−E β 0 β

β α−E β 0
=0
0
β α−E β
β 0 β α−E

Cyclobutadiene

α−E β 0 β

β α−E β 0
=0
0
β α−E β
β 0 β α−E
which leads to

α−E β 0 β β 0 β α−E β

(α − E ) β α−E β −β 0
α−E β +0−β 0
β α−E = 0

0 β α−E β β α−E β 0 β

Cyclobutadiene

α−E β 0 β

β α−E β 0
=0
0
β α−E β
β 0 β α−E
which leads to

α−E β 0 β β 0 β α−E β

(α − E ) β α−E β −β 0
α−E β +0−β 0
β α−E = 0

0 β α−E β β α−E β 0 β
The roots are
E1 = α + 2β, E2 = E3 = α, E4 = α − 2β

Cyclobutadiene: correlation diagram

With the obtained energies sorted in increasing order, the correlation dia-
gram looks like this
|ψ > , ε = α − 2β
4 4
2p z |ψ 2,3 > , ε 2,3 = α
|ψ 1 > , ε 1 = α + 2β

Butadiene

Butadiene
Delocalized system: 2 electrons in |ψ1 i , ε1 = α + 2β, one electron in

|ψ2 i , ε2 = α and one electron in |ψ3 i , ε3 = α

Butadiene

localized system: 2 electrons in one π bond and two electrons in pz orbitals:

Butadiene

Ed = 2(α + 2β) + 2α − {2(α + β) + 2α} = 0
Hückel’s method predicts a triplet ground state with no delocalization

energy for cyclobutadiene!

Butadiene

Ed = 2(α + 2β) + 2α − {2(α + β) + 2α} = 0
Hückel’s method predicts a triplet ground state with no delocalization

energy for cyclobutadiene! The Jahn–Teller effect (we will study it in the
group theory part of this course) leads to a singlet ground state.

Cyclobutadiene molecular orbitals

The molecular orbitals for cyclobutadiene are obtained following the same
procedure as for the allyl system and for butadiene:

Cyclobutadiene molecular orbitals

The molecular orbitals for cyclobutadiene are obtained following the same
procedure as for the allyl system and for butadiene:
|ψ4 i = 0.5 |ψ2pz (1)i − 0.5 |ψ2pz (2)i + 0.5 |ψ2pz (3)i − 0.5 |ψ2pz (4)i , E4 = α − 2β
|ψ3 i = 0.5 |ψ2pz (1)i − 0.5 |ψ2pz (2)i − 0.5 |ψ2pz (3)i + 0.5 |ψ2pz (4)i , E3 = α
|ψ2 i = 0.5 |ψ2pz (1)i + 0.5 |ψ2pz (2)i − 0.5 |ψ2pz (3)i − 0.5 |ψ2pz (4)i , E2 = α
|ψ1 i = 0.5 |ψ2pz (1)i + 0.5 |ψ2pz (2)i + 0.5 |ψ2pz (3)i + 0.5 |ψ2pz (4)i , E1 = α + 2β

Molecular orbitals for cyclobutadiene
|ψ1 i |ψ4 i

Thank you

Huckel

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The Hückel method: Applications to

allyl, butadiene and cyclobutadiene

Grupo de Quı́mica–Fı́sica Teórica θ–φ τ

May 31, 2013

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 1 / 50

We derived in class the molecular Hamiltonian under the Born–Oppenheimer

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 3 / 50

We derived in class the molecular Hamiltonian under the Born–Oppenheimer

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 3 / 50

We derived in class the molecular Hamiltonian under the Born–Oppenheimer

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 3 / 50

We derived in class the molecular Hamiltonian under the Born–Oppenheimer

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 3 / 50

Schrödinger’s equation with this Hamiltonian

is a second order differential equation in partial derivatives with non–separable

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 4 / 50

Schrödinger’s equation with this Hamiltonian

is a second order differential equation in partial derivatives with non–separable

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 4 / 50

Schrödinger’s equation with this Hamiltonian

is a second order differential equation in partial derivatives with non–separable

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 4 / 50

No analytical solutions? No problem!

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 5 / 50

No analytical solutions? No problem! we invent them.

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 5 / 50

No analytical solutions? No problem! we invent them.

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 5 / 50

No analytical solutions? No problem! we invent them.

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 5 / 50

No analytical solutions? No problem! we invent them.

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 5 / 50

Linear Combination of Atomic Orbitals (LCAO)

Linear Combination of Atomic Orbitals (LCAO)

Linear Combination of Atomic Orbitals (LCAO)

Linear Combination of Atomic Orbitals (LCAO)

c1 (H11 − ES11 ) + c2 (H12 − ES12 ) + · · · + cn (H1n − ES1n ) = 0

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 7 / 50

c1 (H11 − ES11 ) + c2 (H12 − ES12 ) + · · · + cn (H1n − ES1n ) = 0

Which can be compactly written as

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 7 / 50

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 8 / 50

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 8 / 50

Hij = hφi |H| φj i Sij = hφi |φj i

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 8 / 50

Hij = hφi |H| φj i Sij = hφi |φj i

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 8 / 50

Hückel method generalities

In its original version, the method was developed to treat

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 9 / 50

Hückel method generalities

In its original version, the method was developed to treat

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 9 / 50

Hückel method generalities

In its original version, the method was developed to treat

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 9 / 50

Hückel method generalities

In its original version, the method was developed to treat

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 9 / 50

Hückel method generalities

In its original version, the method was developed to treat

Albeiro Restrepo (UdeA) Hückel method May 31, 2013 9 / 50