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The Born-Oppenheimer Approximation

Chem5350

Born and Oppenheimer pointed out that since nuclei are thousands of

M OLECULAR S TRUCTURE times more massive than electrons, they move much more slowly and

can be treated as being stationary in considering the motions of

electrons in molecules.

Professor Angelo R. Rossi Thus, a simpler electronic Schrödinger equation can be solved for each

fixed internuclear distance R.

http://homepages.uconn.edu/rossi The molecular vibrations can then be obtained by solving a Schrödinger

Department of Chemistry, Room CHMT215 equation for the motion of the nuclei in the average potential field

The Univerity of Connecticut produced by the electrons.

angelo.rossi@uconn.edu

discussed in some detail as an introduction to the treatment of more

complicated molecules.

Ĥψ(rr 1 , R A , R B ) = Eψ(rr 1 , R A , R B )

r 1 is the vector locating the electron, and R A and R B are the vectors

locating the nuclei in a coordinate system.

labeled A and B

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 3 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 4

The Hydrogen Molecule Ion H2 + The Hydrogen Molecule Ion H2 +

The Hamiltonian for the hydrogen molecule ion is given by The Schrödinger equation for the electronic motion is then

~ 2 ~2 e2 e2 e2 Ĥψe = Ee (R)ψe

Ĥ = − 2M (∇2A + ∇2B ) − ∇2

2me e

− 4πǫ0 r1A

− 4πǫ0 r1B

− 4πǫ0 R

where M is the mass of each nucleus, me is the mass of the electron, with the Hamiltonian for electronic motion given by

r1A is distance between the electron and nucleus A, and r1B is distance ~2 2 e2 e2 e2

between the electron and nucleus B, Ĥe = − ∇e − − −

2me 4πǫ0 r1A 4πǫ0 r1B 4πǫ0 R

The Born-Oppenheimer approximations is introduced to solve the

Schrödinger equation for the H2 + ion. containing the electronic kinetic energy, the electrostatic attractions of

the electrons to each nucleus, and the nuclear electrostatic repulsion.

The nuclear repulsion term is a constant since the internuclear distance

ψ(rr 1A , r 1B , R A , R B ) = ψe (rr A , r B , R ) × ψn (R

RA , R B ) R is fixed, and the electronic Schrödinger equation can be solved for all

R, giving the electronic energy Ee (R) as a function of R.

where ψn (R

R A , R B ) is the wave function for nuclear motion.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 5 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 6

The Born-Oppenheimer approximation shows that the nuclei move in The variational method provides an upper bound to the ground-state

the potential energy Ee (R) determined by the electronic motion, so the energy of a system.

Schrödinger equation for nuclear motion becomes

The ground-state wave function ψ0 and energy E0 satisfy the

~2 Schrödinger equation

− (∇2A + ∇2B ) + Ee (R) ψn (R

R A , R B ) = En ψn (R

RA , R B ) Ĥψ0 = E0 ψ0

2M

Multiply the above equation from the left by ψ0∗ and integrate over all

where En is the energy of nuclear motion which contains contributions

space to obtain

for translational, rotational, and vibrational motion. R ∗

ψ Ĥψ0 dτ

E0 = R 0 ∗

The wave function for nuclear motion ψn (R R A , R B ) is the product of the ψ0 ψ0 dτ

wave functions for translational, rotational, and vibrational motions. The denominator is not set equal to unity to allow for the possibility that

ψ0 is not normalized.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 7 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 8

The Variational Method The Variational Method

A theorem says that if we substitute another function φ for ψ0 and The variational principle states that an upper bound to E0 can be

calculate the corresponding energy according to calculated by using any trial function we wish.

R ∗

φ Ĥφdτ A trial function φ can be chosen such that it depends upon some

Eφ = R ∗ arbitrary parameters, α, β, γ, · · · , called variational parameters.

φ φdτ

then Eφ will be greater than the ground-state energy E0 The energy will also depend upon these variational parameters

This is the variational principle where Eφ ≥ E0 , and the equality holds Eφ (α, β, γ, · · · ) ≥ E0

only if φ = ψ0 , the exact wave function.

Now, Eφ can be minimized with respect to each of the variational

parameters to determine the best possible ground-state energy from

the trial wave function.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 9 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 10

The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

The approach used in solving the Schrödinger equation for the This type of function is referred to as a linear combination of atomic

hydrogen molecule ion is to use a trial wave function made up of orbitals or an LCAO molecular orbital. Since the two nuclei are

hydrogenlike atomic orbitals This approach is called molecular orbital identical, c1 = c2 = c.

theory.

For nuclei that are close, the 1s orbitals overlaps shown below:

Molecular properties calculated in this way are are approximate, but the

treatment can be improved to any desired accuracy.

molecule ion, the following linear combination is used

ψ± = c1 1sA ± c2 1sB

where 1sA and 1sB are atomic hydrogen orbitals on protons A and B,

and c1 and c2 are constants.

The above diagram shows the magnitudes of the 1s wave functions on atoms A and B when they are 3a0

apart but not interacting. The abscissa is the distance from atom A along the internuclear axis in units of a0 .

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 11 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 12

The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

In order to normalize the molecular orbital with the plus sign, the following integral The normalization can be written in terms of the overlap integral

must have the value of unity: Z Z

∗

ψ+ ψ+ dτ = 1

c2 2 + 2 1sA 1sB dτ = c2 (2 + 2S) = 1

Substituting the wave function yields

Z so that

c2 (1s∗A + 1s∗B )(1sA + 1sB )dτ = 1 1

c= 1

Z Z Z Z [2(1 + S)] 2

c2 1s∗A 1sA dτ + c2 1s∗A 1sB dτ + c2 1s∗B 1sA dτ + c2 1s∗B 1sB dτ = 1 The normalized wave function with a plus sign is given by

• The first and last integrals are equal to 1 because the 1s orbitals are normalized. 1

• The second and third integrals are equal because the wave function is real and are ψg = 1 (1sA + 1sB )

called overlap integrals. [2(1 + S)] 2

1

ψu = 1 (1sA − 1sB )

[2(1 − S)] 2

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 13 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 14

The Hydrogen Molecule Ion H2 + : Even and Odd Parity The Hydrogen Molecule Ion H2 + : Even and Odd Parity

When a molecule has a center of symmetry, the wave function may or The parity of an orbital is even (g) if

may not change sign when it is inverted through the center of symmetry. the wave function is unchanged un-

der inversion through the center of

• If ψ(x, y, z) = ψ(−x, −y, −z), the wave function is said to have even symmetry.

parity and is designated with a subscript g for gerade. The parity of an orbital is odd (u) if

the wave function changes sign un-

• If ψ(x, y, z) = −ψ(−x, −y, −z), the wave function is said to have odd der inversion through the center of

parity and is designated with a subscript u for ungerade. symmetry.

Homonuclear diatomic molecules

have a center of inversion while

heteronuclear diatomic molecules do

not.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 15 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 16

The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

internuclear distance R, and the result is given below

R2

S = e−R 1 + R +

3

increased to infinity, the overlap integral decreases asymptotically to

zero.

and B are separated by 3a0 . (b) Magnitude of the normalized molecular

orbital ψu . (c) Magnitude of ψg2 . (d) Magnitude of ψu2 .

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 17 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 18

The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

Using the molecular orbitals (ψg or ψu ), the upper bound to the energy The integral HAA is called the Coulomb integral because the

of H2 + can be calculated using the variation principle: difference between HAA and the energy of a single hydrogen atom is

R ∗ R just that of the Coulomb interaction of nucleus B with an electron

R

ψ Ĥψdτ [c1 1sA + c2 1sB ]Ĥ[c1 1sA + c2 1sB ]dτ

R centered on nucleus A.

E= =

ψ ∗ ψdτ [c1 1sA + c2 1sB ]2 dτ Z

e2 e2

HAA = E1s + − J, where J = 1sA 1sA dτ

c21 HAA + 2c1 c2 HAB + c22 HBB c21 HAA + 2c1 c2 HAB + c22 HBB 4πǫ0 R 4πǫ0 rB

E= =

c21 SAA + 2c1 c2 SAB + c22 SBB c21 + c1 c2 S + c22

R R J is called the electron repulsion integral

HAA = 1sA Ĥ1sA dτ = 1sB Ĥ1sB dτ = HBB

R R 1

HABR = 1sA Ĥ1sBRdτ = 1sB Ĥ1sA dτ J = e−2R 1 +

SAA = 1sRA 1sA dτ = 1sRB 1sB dτ = SBB = 1 R

SAB = 1sA 1sB dτ = 1sB 1sA dτ = S

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 19 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 20

The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

The integral HAB is referred to as the resonance integral. To find the minimum energy. the derivatives of E with respect to c1 and

Z c2 are set to zero.

e2 e2

HAB = SAB E1s + − K, where K = 1sB 1sA dτ To do this, the equation for the energy of H2 + is set rewritten in the form:

4πǫ0 R 4πǫ0 rB

K is called the exchange integral. E(c21 + 2c1 c2 S + c22 ) = c1 HAA + 2c1 c2 HAB + c22 HBB

K= − e−R (1 + R)

R

∂E 2

E(2c1 + 2c2 S) + (c + 2c1 c2 S + c22 ) = 2c1 HAA + 2c2 HAB

∂c1 1

and differentiating this equation with respect to c2 equals

∂E 2

E(2c1 S + 2c2 ) + (c + 2c1 c2 S + c22 ) = 2c1 HAB + 2c2 HBB

∂c2 1

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 21 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 22

The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

Since ∂c

∂E

and ∂c

∂E

are equal to zero for the minimum energy, the above The energy ∆Eg of the H2 + ion in the bonding orbital ψg relative to the

1 2

equations can be written as completely dissociated species H+ and H is given by

∆g = Eg − E1s =

c1 (HAB − SE) + c2 (HBB − E) = 0 1+S

There is a nontrivial solution to these equations only if the determinant The energy ∆Eu of the H2 + ion in the antibonding orbital ψu relative to

of the coefficients is equal to zero the completely dissociated species H+ and H is given by

J −K

HAA − E HAB − SE ∆u = Eu − E1s =

HAB − SE HBB − E = 0 1−S

J+K

Eg = E1s + 1+S

J−K

Eu = E1s + 1−S

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 23 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 24

The Hydrogen Molecule Ion H2 + : Theory vs Experiment The Hydrogen Molecule Ion H2 + : Potential Energy Curves

Calculated Experimental

Equilibrium Separation (Re ) 2.50 a0 = 1.32 Å 1.06 Å

Binding Energy (kJ mol−1 ) 170 258

The simple molecular orbital wave function which was chosen does not

quantitatively explain the bonding in the hydrogen molecule ion, but this Calculated and experimental molec-

wave function can be improved by adding more terms. ular potential energy curves for H2 +

showing the variation of energy as

The next step is to add terms for the 2s and 2p orbitals on the two

the bond length is changed.

nuclei.

ψ = c(1sA + 1sB ) + c′ (2sA + 2sB ) + c′′ (2pzA + 2zB )

In the limit of adding more terms, the results obtained from the solution

of the Schródinger equation are in good agreement with experiment.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 25 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 26

The Hydrogen Molecule Ion H2 + : Orbital Interaction Diagram Molecular Orbital Description of the H2 Molecule

It is useful to represent the energies of molecular orbitals by use of an Using the Born-Oppenheimer approximation, the electronic Hamiltonian

orbital interaction diagram for the hydrogen molecule may written as

~2 e2 1 1 1 1 1 e2

Ĥ = − (∇21 + ∇22 ) + − − − − + +

2me 4πǫ0 rA1 rA2 rB1 rB2 r12 4πǫ0 R

• Since HAA and HBB are negative, and S is positive, Eg is more negative than Eu

and is the energy of the more stable molecular orbital.

• Since ψg is symmetrical around the internuclear axis, it is referred to as a σ, since

it is even, it is referred to as gerade, and since it is made up of two 1s orbitals, it is

designated as σg 1s.

• The less stable orbital is represented by the σu∗ 1s.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 27 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 28

Molecular Orbital Description of the H2 Molecule Molecular Orbital Description of the H2 Molecule

When the electronic Hamiltonian for the hydrogen molecule is used in Each electron can be assigned to an orbital, and the electronic wave

function for the molecule is the product of two wave functions for the two

Ĥψe = Ee (R)ψe electrons:

ψM O = ψi (1)ψj (2)

An exact solution cannot be obtained because of the 1

r12

term.

where i and j designate the different orbitals, and 1 and 2 designate the

This is the reason that the LCAO-MO method is used to obtain an

two electrons.

approximate solution.

According to the Pauli principle, two electrons with opposite spin can be

According to the LCAO-MO approach, molecular hydrogen is formed by

assigned to a given spatial orbital.

putting two electrons with opposite spin in the σg 1s orbital.

As a first approximation, we will assume that in the ground state of the

hydrogen molecule, the two electrons are placed in a σg orbital.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 29 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 30

The electronic configuration of H2 will be described as (1σg )2 . The approximate energy of the hydrogen molecule is obtained by

The wave function for electron 1 in the 1σg molecular orbital is calculating the expectation of the Hamiltonian using this wave function

represented by Z

∗ 2 2

E = ψM O [(1σg ) ]Ĥel ψM O [(1σg ) ]dτ

1

1σg (1) = 1 [1sA (1) + 1sB (1)]

[2(1 + S)] 2

Calculated Experimental

The wave function satisfying the antisymmetric requirement is given by Equilibrium Separation (Re ) 0.84 Å 0.741 Å

a Slater determinant, and so the approximate wave function for the Dissociation Energy (kJ mol−1 ) 255 458

ground state of the hydrogen molecule is given by the following Slater

determinant: Although simple MO theory does account for a large proportion of the

binding energy of the H2 molecule, it has to be extended to yield

1 1σ (1)α(1) 1σg (1)β(1) accurate results.

ψM O [(1σg )2 ] = √ g

2 1σg (2)α(2) 1σg (2)β(2)

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 31 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 32

Deficiency in the Approximate MO Wave function Deficiency in the Approximate MO Wave function

One can see the deficiency in the approximate wave function by Schematic E(R) curves for the LCAO-MO (red

curve) and exact (blue curve) for H2 .

multiplying out the spatial part:

Note that the LCAO-MO curve dissociates to a

mixture of neutral and ionic species.

1s (1)1s (2) + 1s (1)1sB (2) + 1sB (1)1sA (2) + 1sB (1)1sB (2)

| A {z A } | A {z } | {z } The MO curve shows that the model does not

correctly describe H2 in the limit of large R.

ionic covalent ionic

The horizontal dashed line is the zero of en-

• The first and last term correspond to forms of the hydrogen ergy corresponding to two H atoms at infinite

separation.

molecule with ionic bonding: H− + + −

A HB and HA HB . The improved results are given in the table be-

• Thus, at R = ∞, the molecular orbital wave function describes a low:

state which is 50 % H+ + H− and 50 % H · +H· which is clearly not

correct. Equilibrium Separation (Re ) 0.749 Å 0.741 Å

• This problem can be reduced by introducing variable coefficients c1 Dissociation Energy (kJ mol−1 ) 386 458

and c2 in

The inclusion of one variational parameter

ψ = c1 (R)ψcovalent + c2 (R)ψionic leads to significant improvement.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 33 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 34

Molecular Orbitals for Many-Electron Atoms Molecular Orbitals for Many-Electron Atoms

In MO theory, an electron is associated with a wave function that is Each of the entries in the Slater determinant is an MO that is expressed

delocalized over the entire molecule. as a linear combination of AOs denoted by φi :

The MOs (σi ) are constructed from linear combinations of atomic X

orbitals (AOs) leading to the term LCAO-MO Model. σi (1) = cij φj (1)

j

The many-electron molecule must satisfy the Pauli exclusion principle

leading to the expression of a wave function of an n-electron molecule The sum extends over AOs on all the atoms in a molecule, and the

as a Slater determinant number in parentheses refers to the electron under consideration.

For example, in H2 , both electrons are in the σ1 molecular orbital

σ1 (1)α(1) σ1 (1)β(1) . . . σm (1)β(1)

1 σ1 (2)α(2) σ1 (2)β(2) . . . σm (2)β(2)

ψ(1, 2, 3, . . . , n) = √ σ1 (1) = (φ1,1sA + φ1,1sB )

n! . . . ... ... ...

σ1 (n)α(n) σ1 (2)β(2) . . . σm (n)β(n)

where m = n

2

if n is even, and m = n+1

2

if n is odd.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 35 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 36

How Are Observables for Molecules Calculated? Computing Molecular Orbital Energies

Observables for a diatomic molecule such as the dipole moment, the Although the optimization of the cij is best carried out by a computer, we can carry out

bond dissociation energy, the bond length, and the ionization energy are a simple calculation by having one atomic orbital on each atom:

ultimately all related to the MOs and to the expansion coefficients cij . σ1 = c11 φ1 + c12 φ2

Therefore, we need a method to determine the cij in a given MO. where φ1 and φ2 are AOs on the different atoms.

• Assume that the atomic orbitals have been chosen. To determine the optimal values for these coefficients, the MO energy is minimized

• The variational method is used to determine the optimal values for with respect to the values of the AO coefficients.

cij . The expectation value of the energy is given by

R ∗

<ǫ> = Rσ1 ∗Ĥσ1 dτ

σ1 σ1 dτ

R

= R [c11 φ1 +c12 φ2 ]Ĥ[c11 φ1 +c12 φ2 ]dτ

(c11 φ1 +c12 φ2 )∗ (c11 φ1 +c12 φ2 )dτ

R R R

(c11 )2 φR1∗ Ĥφ1 dτ +(c21 )2 Rφ2∗ Ĥφ2 dτ +2c11 c21R φ∗1 Ĥφ2 dτ

= (c11 )2 φ∗ 2 φ∗ φ∗

1 φ1 dτ +(c12 ) 2 φ2 dτ +2c11 c12 1 φ2 dτ

<ǫ> = (c11 )2 +(c12 )2 +2c11 c12 S12

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 37 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 38

Solving for Molecular Orbital Energies and Coefficients MO ǫi and cij for Homonuclear Diatomic Molecules

To find the minimum energy, the derivatives of ǫ with respect to c11 and c21 are set to For a homonumclear diatomic molecule such as H2 , Be2 , · · · , F2 , H11 = H22

zero. leading to the following two solutions

Differentiating this equation with respect to c11 and c12 equals H11 +H12

ǫ1 = 1+S12

∂ǫ ǫ2 = H11 −H12

(2c11 + 2c12 S12 )ǫ + ((c11 )2 + (c12 )2 + 2c11 c12 S12 ) = 2c11 H11 + 2c12 H12 1−S12

∂c11

ǫ1 and ǫ2 correspond to the bonding and antibonding MO energies, respectively.

∂ǫ

(2c12 + 2c11 S12 )ǫ + ((c11 )2 + (c12 )2 + 2c11 c12 S21 ) = 2c12 H22 + 2c11 H12 The ǫi can be obtained from the following formulas:

∂c12

Since ∂ǫ

∂c11and ∂ǫ

∂c21 are equal to zero for the minimum energy, the above equations • Assume H11 and H22 can be approximated by the ionization energy of the neutral

can be written as atom. √

• H12 can be calculated using the approximation: H12 = −1.75S12 H11 H22

c11 (H11 − ǫ) + c12 (H12 − ǫS12 ) =0

c11 (H12 − ǫS12 ) + c12 (H22 − ǫ) =0 The coefficients cij can then be obtained from the following equations:

There is a nontrivial solution to these equations only if the determinant of the

c11 (H11 − ǫ) + c12 (H12 − ǫS12 ) =0

coefficients is equal to zero

c11 (H12 − ǫS12 ) + c12 (H22 − ǫ) =0

H11 − ǫ H12 − ǫS12

H12 − ǫS12 H22 − ǫ =0

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 39 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 40

The H2 + and H2 Molecules Heteronuclear Diatomic Molecule: HF

For both the H2 + and H2 molecules, H11 = In this case H11 6= H22 .

H22 = -13.6 eV, the ionization energy of H. Let φ1 be a hydrogen 1s orbital with

A reasonable value is assumed for the over- H11 = -13.6 eV, and let φ2 be a fluo-

lap: S = 0.30. Using these values yields rine 2pz orbital with H22 = -18.6 eV.

ǫ1 = -16.0 eV and ǫ2 = -9.2 eV. The two MOs have the form

• The energy of the bonding orbital is low- σ1 = C11 φH1s + c12 φF 2pz

ered relative to H11 by 2.4 eV. σ2 = C21 φH1s + c22 φF 2pz

• The energy of the antibonding orbital is

raised relative to H11 by 4.4 eV. Given an overlap S = 0.30, H12 =

-8.35 eV.

The MO energy results for H2 can be con-

Solving the equation for the energies

veniently summarized in a molecular orbital

gives ǫ1 = -19.6 eV (the bonding

energy diagram.

MO), and ǫ2 = -10.3 eV (the anti-

bonding MO).

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 41 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 42

The HF Molecule: Obtaining Coefficients for the MOs Obtaining MO Coefficients for the HF Molecule

c11 (H11 − ǫ1 ) + c12 (H12 − ǫ1 S12 ) = 0 c21 (H11 − ǫ1 ) + c22 (H12 − ǫ1 S12 ) = 0

Substitution of the appropriate values gives Substitution of the appropriate values gives

c11 (-13.6 + 19.6) + c12 (-8.35 + 0.30 x 19.6) = 0 c21 (-13.6 + 10.3) + c22 (-8.35 + 0.30 x 10.3) = 0

c11 c21

= 0.41 = -1.58

c12 c22

Using this result in the normalization equation Using this result in the normalization equation

c211 + c212 + 2c11 c12 S12 = 1 c221 + c222 + 2c21 c22 S12 = 1

yields c11 = 0.34, c12 = 0.84 and σ1 = 0.34φH1s + 0.84φF 2pz . yields c21 = 0.99, c22 = -0.63 and σ2 = 0.99φH1s − 0.64φF 2pz .

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 43 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 44

Obtaining MO Coefficients for the HF Molecule The Molecular Orbital Energy Diagram

The relative magnitude of the coefficients of the AOs gives information about the By convention, the AOs for the atoms are shown on

charge distribution in the molecule. the left and right side of the diagram.

The MOs are generated by combining the AOs are

Consider an electron in the bonding MO of HF given by σ1 = 0.34φH1s + 0.84φF 2pz . shown in the middle.

The probability density of this orbital can be calculated as

The molecular energy diagram allows us to deter-

Z Z mine the energies of the MOs relative to the AOs.

|ψ 2 |dτ = σ1∗ σ1 dτ = c211 + c212 + 2c11 c12 S12 = 1 The bonding MO is lower in energy than the lower

of the two AOs, and the antibonding MO is higher in

energy than the higher of the two AOs.

This gives

Empirical rules can be used to obtain a reasonable

• c211 + c11 c12 S12 = 0.21 is the probability of finding the e− around the H atom. size basis set to describe the electronic structure of

first and second row diatomic molecules at a quan-

• c212 + c11 c12 S12 = 0.79 is the probability of finding the e− around the F atom. titative level.

• 2c11 c12 S12 = 0.17 is the probability that is shared between the H and F atoms.

For H and He, only 1s orbitals are used; for Li → Ne,

the 2s, 2px , 2py , and 2pz atomic orbitals included

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 45 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 46

Only orbitals of the same symmetry will combine with one another.

The adjacent figure indicates how over-

Nonzero overlap between two AOs occurs lap varies with distance for different or-

• if both AOs are cylindrically symmetric with respect to the molecular bitals.

axis (σ MOs) or As discussed earlier, a nonzero overlap

• if both AOs have a common nodal plane that coincides with the of atomic orbitals is necessary for chemi-

molecular axis (π orbitals). cal bond formation.

bitals is maximized when R = 0, but the

overlap of an s orbital with a pz orbital has

it maximum value at a larger internuclear

distance.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 47 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 48

Symmetry Operations for Diatomic Molecules Molecular Orbitals for Homonuclear Diatomic Molecules

All MOs of diatomic molecules can be divided into two groups with regard to rotation

about the molecular axis.

• If this rotation leaves the MO unchanged, the MO has σ symmetry. Combining s

orbitals always gives rise to σ MOs for diatomic molecules.

• If the molecule has one nodal plane containing the molecular axis, the MO has π

symmetry. Combining πx or πy AOs always gives rise to π MOs.

The second operation of inversion through the center of the molecule is valid only

for homonuclear diatomic molecules.

• If this operation leaves the molecule unchanged, the MO has g symmetry:

σ(x, y, z) → σ(−x, −y, −z).

• If σ(x, y, z) → −σ(−x, −y, −z), the MO has u symmetry.

arrows show the transformation σ(x, y, z) → σ(−x, −y, −z).

If the amplitude changes sign under this transformation, it has u

symmetry. If it is unchanged, it has g symmetry.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 49 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 50

Symmetry Labels for Homonuclear Diatomic Molecules σ and π Orbitals for Diatomic Molecules

homonuclear diatomic molecules. Two types of MOs can be generated from

2p AOs.

1. The MOs are classified according to increasing energy.

For example, a 2σg orbital has the same symmetry, but a higher 1. If the axis of the 2p orbital lies on

energy than the 1σg orbital. the intermolecular axis (by conven-

tion the z-axis), a σ MO is generated.

2. The MOs are classified by the AOs from which they were This specific MO is called 3σg or

σg (2pz ).

generated.

Thus, the σg (2s) MO has a higher energy than the σg (1s) MO. 2. Combining 2px or 2py orbitals on

each atom gives a π MO because the

A superscript ∗ is used to designate antibonding MOs for both MO has a nodal plane containing the

molecular axis.

classifications.

These MOs are degenerate in

energy and are called 1πu or

πu (2px ), πu (2py ) MOs.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 51 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 52

Mixing Atomic Orbitals to Form Molecular Orbitals Labeling Molecular Orbitals of Diatomic Molecules

In principle, it is possible to take a linear combination of all the basis The MOs that used to describe chemical bonding in first and second

functions of the same symmetry (either σ or π) when constructing MOs. row homonuclear diatomic molecules is shown in the table below.

However, an additional criterion based on orbital energies, reduces the The AO that is the major contributor to the MO is shown in the last

number of AOs which mix into a given MO. column, and the minor contribution is shown in parenthesis.

• For example, the mixing between 1s and 2s AOs for second row

diatomics can be neglected at our level of discussion.

• However, for these same molecules, the 2s and 2pz AOs both have σ

symmetry and will mix if their energies are not significantly different.

going from Li → F, the s-p mixing decreases for second-row diatomics

in the order Li2 , B2 , . . . , O2 , F2 .

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 53 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 54

It is useful to think of MO formation as a two step process: The interaction of 1s orbitals on each

atom gives rise to a bonding and anti-

1. create separate MOs from the 2s and 2p AOs. bonding MO as shown schematically in

the adjacent figure.

2. combine the MOs of the same symmetry to create the final MOs

that include s − p mixing. Each MO can hold two electrons of oppo-

site spin.

For the sequence H2 → N2 , the orbital energies increase in the The configurations of H2 and He2 are

sequence (1σg )2 and (1σg )2 (1σu∗ )2 , respectively.

For H2 both electrons are in the 1σg or-

1σg < 1σu∗ < 2σg < 2σu∗ < 1πu < 3σg < 1πg∗ < 3σu∗ bital which is lower than the 1s AOs.

In the MO model for He2 , there are two

Moving across the periodic table to O2 and F2 , the order of the 1πu and electrons each in the 1σg and 1σu∗ or-

the 3σg changes. bitals. Because the 1σu∗ is greater than

zero, He2 is not a stable molecule in this

1σg < 1σu∗ < 2σg < 2σu∗ < 3σg < 1πu < 1πg∗ < 3σu∗ model.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 55 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 56

Schematic MO Energy Diagram for the Valence Electrons in F2 Schematic MO Energy Diagram for the Valence Electrons in N2

F2 has s and p valence electrons, but the N2 also has s and p valence electrons, but unlike

s − p mixing can be neglected because F2 , the s − p mixing is not negligible because the 2s

AO lies below the 2p AO by only 12.4 eV.

the 2s AO lies 21.6 eV below the 2p AO.

Therefore, the 2σ and 3σ MOs have significant con-

The configuration for F2 is tributions from both the 2s and 2pz AOs.

The configuration for N2 is

(1σg )2 (1σu )2 (2σg )2 (2σu∗ )2 (3σg )2 (1πux )2 (1πuy )2 (1πgx

∗ 2 ∗ 2

) (1πgy )

∗ 2

(1σg )2 (1σu )2 (2σg )2 (2σu ) (1πux )2 (1πuy )2 (3σg )2

For this molecule, the 2σ MO is essen-

tially described by a single 2s AO on Note that the mixing has changed the shape of the

2σ and 3σ MOs of N2 .

each atom while the 3σ MO is described

The 2σu ∗ has become less antibonding, and the 3σ

quite well by a single 2pz AO on each MO has become less bonding for N2 in comparison

g

slightly offset in energy. The degenerate p and π are shown slightly offset in

energy.

The dominant contributions in energy are

The dominant contributions in energy are shown in

shown in solid lines, and minor contribu- solid lines, and minor contributions of s − p mixing

tions of s − p mixing are neglected. are neglected.

From the overlaps of the MOs, the triple bond in N2

arises from the occupation of the 3σg , 1πux , and

1πuy MOs.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 57 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 58

MO Energy Levels for Second-Row Homonuclear Diatomics Bond Order, Bond Energy, and Bond Length

The MOs are filled in sequence of increasing en- The concept of bond order can be defined as

ergy, and the number of unpaired electrons for a

diatomic molecule can be predicted.

total bonding electrons−total antibonding electrons

The energy of the MOs tends to decrease with in- bond order = 2

creasing atomic number which is a result of larger

effective charge and smaller atomic size lower-

ing the corresponding AO energies. The bond energy is expected to be very small for a bond order of zero.

The 3σg orbital energy falls more rapidly than the The trend in bond energies and force constants shows the same trend as the bond

1πu orbital because the s − p energy splitting in-

orders.

creases in going from Li2 to F2 .

The mixing which occurs between the 2pz orbitals For a given atomic radius the bond length is expected to vary inversely with bond

composing the 3σg orbital and the 2s orbitals of the order.

2σg decreases.

Because the 2px and 2py AOs don’t mix with the 2s • The trend is approximately followed for the series Be2 → N2 .

AO, the 1πu remains constant across this series of

atoms resulting in a switch in the energy ordering of • The trend is not followed for H2 → Li2 because the atomic orbital changes from 1s

the 3σg and 1πu MOs for O2 and F2 . to 2s and because the He2 molecule is not really bonded.

Both B2 and O2 are predicted to have two unpaired

electrons and, thus, to have a net magnetic moment

(paramagnetic molecule) which is in good agree-

ment with experiment.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 59 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 60

Bond Order, Bond Energy, and Bond Length Heteronuclear Diatomic Molecules

By looking at the trend in bond orders,

MO theory can provide an understand-

diatomic molecules is considered.

ing of the trends in the binding en-

ergies, bond lengths, and vibrational 1. When two interacting AOs of different energies interact, the

force constants for diatomic molecules. coefficients of the AOs in the MOs have different magnitudes.

As the number of electrons increases,

• The coefficient of the lower energy AO is greater than that of

the bond energy has a pronounced max-

imum for N2 and a smaller maximum for the higher AO in the bonding MO.

H2 . • The opposite is true for the antibonding MO.

The bond length also increases in the se- 2. The g and u symmetries do not apply and the MOs are numbered

ries H2 → F2 , but exhibits a more compli- differently:

cated trend for smaller molecules.

The vibrational force constant k shows Homonuclear 1σg 1σu∗ 2σg 2σu∗ 1πu 3σg 1πg∗ 3σu∗ . . .

the same trend as the bond energy Heteronuclear 1σ 2σ 3σ 4σ 1π 5σ 2π 6σ . . .

above.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 61 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 62

The Molecular Orbital Energy Diagram for HF Hückel MO Theory for Conjugated Molecules

• acyclic polyene: Cn Hn+2

• monocyclic polyene: Cn Hn

The 2s electrons are almost completely • polycyclic polyenes: Cn Hn−2 , Cn Hn−4 , . . .

localized on the F atom.

The 1π electrons are completely local- Electronic Configurations of Carbon and Hydrogen

ized on the F atom because the 2px and 6 C: 1s2 2s2 2p2 - the C atom contributes four valence electrons.

2py orbitals have a zero overlap with the

1 H: 1s - the H atom contributes one valence electron.

Schematic energy diagram showing 1

the AO and MO orbital energy 1s orbitals of H.

levels for the valence electrons in

The admixture of s and p in the 4σ and

Octet Rule

HF.

5σ ∗ MOs changes the electron distribu- Atoms other than H tend to be surrounded by 8 electrons either through

The 3σ, 4σ, and 1π MOs for HF can tion somewhat when compared with a bonding or sharing.

be described as follows: homonuclear diatomic molecule.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 63 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 64

Hückel MO Theory for Conjugated Molecules Hückel MO Theory for Planar Conjugated Molecules

Lewis Structure of C2 H4 We are primarily interested in obtaining the electronic energies and wave functions for

planar unsaturated molecules like benzene.

C2 H4 - total valence electrons = 4 × 1 + 2 × 4 = 12

ĤΨ = EΨ

In planar unsaturated molecules, the π MOs will not mix with the σ MOs because of

Ψ = ψσ × ψπ

We will be mainly concerned with the pz orbitals, since they are the Ĥ = Ĥσ + Ĥπ + Ĥσ π

predominant influence on reactivity.

We assume that we know ψσ and can then treat the σ system as merely providing part

The underlying σ electrons provide an effective potential for the π of the effective potential in which the π electrons move.

electrons.

Hπef f (σ)ψπ = Eπ ψπ where Ĥπef f (σ) = Ĥπ + Eσ

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 65 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 66

Hückel MO Theory for Ethylene Variational Principle for Hückel Model Applied to Ethylene

R

In general, for n carbon atoms, there are n basis functions or n × pz ψj Ĥπef f ψj dτ

orbitals: ǫj = R

Xn ψj ψj dτ

ψj = crj φr

(c11 φ1 + c21 φ2 )Ĥπef f (c11 φ1 + c21 φ2 )dτ

r=1 ǫj = R

(c11 φ1 + c21 φ2 )(c11 φ1 + c21 φ2 )dτ

where ψj is MO j.

Thus, The following definitions are given

Hπ ψj MO = ǫj ψj MO R R

H11 = R φ1 Ĥπef f φ1 dτ H12 = R φ1 Ĥπef f φ2 dτ

As an example, the ethylene wave functions (ψπ , ψπ∗ ) are taken as S11 = φ1 φ1 dτ S12 = φ1 φ2 dτ

linear combinations of pz orbitals on each carbon center (LCAO-MO).

∂ǫj

∂c11

= 0 : c11 (H11 − ǫj S11 ) + c21 (H12 − ǫj S12 ) = 0

ψ1 (ψπ ) = c11 φ2pz1 + c21 φ2pz2 ψ2 (ψπ∗ ) = c21 φ2pz1 + c22 φ2pz2 ∂ǫj

∂c21

= 0 : c21 (H11 − ǫj S12 ) + c22 (H22 − ǫj S22 ) = 0

where φ2pz1 and φ2pz2 are pz orbitals on C1 and C2 , respectively.

H11 − ǫj S11 H12 − ǫj S12 c11

=0

H21 − ǫj S12 H22 − ǫj S22 c21

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 67 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 68

The Hückel Approximation The Hückel Approximation for Ethylene

Hrr = φr Ĥφr dτ = α Coulomb Integral

α−ǫ β

( =0

R β α−ǫ

β, r bonded to s

Hrs = φr Ĥφs dτ = Resonance Integral

0, otherwise

Solution of this determinant leads to the following results:

(

R 1, if r = s • The energies of the two MOs are ǫ = α ± β.

Srs = φr φs dτ = Overlap Integral √

0, if r 6= s

• c11 = c21 = 1/ 2 for ǫ = α + β

√

According to the Hückel approximation, the previous set of linear • c11 = −c21 = 1/ 2 for ǫ = α − β

equations for ethylene become:

The parameter α plays the role of reference energy because it is the

energy of a 2pz AO in the absence of delocalization.

α − ǫj β c11

=0

β α − ǫj c21

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 69 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 70

The Hückel Approximation for Ethylene The Hückel Model for the Allyl System

α−ǫ β 0

β α−ǫ β =0

0 β α−ǫ

α−ǫ

β 1 0

1 α−ǫ

1 = 0

β

0 1 α−ǫ

β

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 71 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 72

The Hückel Model for the Allyl System The Hückel Model for the Allyl System

Define

ǫ−α Eigenvalues

−x =

β

√

−x 1 0

ǫ1 = α − 2β

1 −x 1 = 0

0 1 −x ǫ2 = α

The solution of the above determinant leads to the following values for x √

ǫ3 = α + 2β

√

x3 − 2x = 0 x = ± 2, 0

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 73 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 74

The Hückel Model for the Allyl System The Hückel Model for the Allyl System

Eigenvectors Eigenvectors

The following is obtained from the secular equations:

1 2

c11 = c31 = ; c21 = √

− c11 x3 + c21 = 0 2 2

c11 − c21 x3 + c31 = 0

c21 x3 − c31 x3 = 0

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 75 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 76

Generalization of Hückel Model to A Planar Molecule Generalization of Hückel Model to A Planar Molecule

with n Basis Functions with n Basis Functions

H11 − ǫj S11 H12 − ǫj S12 . . . H1n − ǫj S1n c11 R

H21 − ǫj S12 H22 − ǫj S22 . . . H2n − ǫj S2n

c21

Hrr = φr Ĥφr dτ = α Coulomb Integral

.. .. .. =0 (

. . . R β, r bonded to s

Hn1 − ǫj Sn2 Hn2 − ǫj Sn2 . . . Hnn − ǫj Snn cn1 Hrs = φr Ĥφs dτ = Resonance Integral

0, otherwise

HC j = ǫj SC j (

R 1, if r = s

Srs = φr φs dτ = Overlap Integral

0, if r 6= s

H11 ... H1n S11 ... S1n ǫ1 ... 0

. . . . . .. .

H= . . S= . . E= . . .

. . . . . .

Hn1 ... Hnn Sn1 ... Snn 0 ... ǫn The overlap matrix is now a unit matrix:

HC = ESC !

1 ... 0

. .. .

S= .

. . .

.

0 ... 1

HC = EC

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 77 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 78

Generalization of Hückel Model to A Planar Molecule The Hückel Model for the 1,3-Butadiene

with n Basis Functions

Now start with the eigensystem for the Schrödinger equation

The exists a unitary transformation U such that 0 1 0 0

1 0 1 0

H=

0

U† = U−1 , UU−1 = 1 1 0 1

0 0 1 0

Then

−1

UHU UC = E |{z}

| {z } |{z} UC

D C′ C′ Perform diagonalization using mathematical software.

′ ′

DC = EC

λ1 ... 0 ǫ′1 ... 0

. . . . .. .

D = .. .. .. = E = .. . .. λn = ǫ′n = − α−ǫ

β

n

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 79 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 80

The Hückel Model for the 1,3-Butadiene The Hückel Model for the 1,3-Butadiene

occupied

X

Eπ = ν j ǫj

j=1

For Butadiene

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 81 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 82

Charge and Bond Order Matrix Aromaticity of Benzene: Valence Bond Theory

Charge In terms of valence bond theory the benzene molecule is described as a resonance

hybrid of two canonical Lewis structures containing three isolated C=C double bonds.

The π electron density on atom r is given as

Both of these canonical resonance structures are shown below in the figure below:

occupied n

X X

qr = prr = νj c2rj qr = N (Total Number of π Electrons) H

j=1 r=1 H❜

❜✧✧ ✧H

✧❜❜✧ ✧✧❜❜

✧ ✧✧❜

❜❜

✧ ✧ ❜

where νj is the number of electrons (0, 1, 2) in MO j.

✧❜❜

❜ ✧❜ ❜

❜ ✧

Bond Order H ✧ ❜✧ ❜ H ❜✧✧

❜ ❜❜✧

✧✧

ΨI ΨII

occupied

X

prs = νj crj csj For Valence Bond theory, delocaalization energy points to an ambiguity because the

j=1 total wave function is constructed from localized wave functions:

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 83 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 84

Aromaticity of Benzene: Molecular Orbital Theory Delocalized Molecular Orbitals of Benzene and π-Energies

the electron density is smeared out in a π cloud above and below the ring.

This can be emphasized by placing a circle inside the benzene ring

✗✔

✧✧❜❜

✖✕

ΨTotal

❜❜✧✧

The molecular orbitals are considered to delocalized over the entire molecule, and this

extra stability of planar aromatic conjugated hydrocarbons which is called the

resonance delocalization energy can be calculated using Hückel theory.

From experiment it is known that benzene does not have three isolated C-C double

bonds but consists instead of a delocalized π electron system which produces an

extra stability called resonance stabilization energy or aromaticity.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 85 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 86

In general, the heat of hydrogenation of an isolated double bond (essentially an Monocyclic planar systems of trigonally hybridized atoms that contain

ethylene double bond) in butene is about 30.3 kcal/mol. (4n + 2) p-electrons (where n is a non-negative integer) will exhibit

Adding the heat of hydrogenation of localized double bonds appears to be violated aromatic character.

when the double bonds are conjugated.

The rule is generally limited to n = 0 - 5.

• Thus, the heat of hydrogenation for trans-1,3-butadiene is 57.1 kcal/mol compared

with the 60.6 kcal/mol for a pair of ethylene double bonds. This rule is derived from the Hückel MO calculation on planar

• Since the hydrogenation in each case is butane, the energy difference of 3.5

kcal/mol must be due to the greater stability of conjugated double bonds.

monocyclic conjugated hydrocarbons (CH)m where m is an integer

equal to or greater than 3 according to which (4n + 2) p-electrons are

There is a theoretical parallel to the additivity of localized π double bonds versus contained in a closed-shell system.

delocalized π bonds.

The Hückel Molecular Orbital (HMO) energy for butadiene is 4 α + 4.472 β. Systems containing 4n p-electrons such as cyclobutadiene and the

For a pair of isolated double bonds, the Hückel energy of ethylene is doubled to

cyclopentadienyl cation are antiaromatic and are not considered as

obtain 4 α + 4 β. stable.

The HMO method indicates that the double bonds of the butadiene molecule are

stabilized by 0.472 β called the delocalization energy.

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 87 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 88

Hückel (4n + 2 ) Rule Delocalization Energies of Several Cyclic Polyenes

Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 89 Fall Semester 2013 Last Updated: October 20, 2013 at 8:18pm 90

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