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CHEM 6320

Fall 2005

D. Molecular Orbital Theory 1. Introduction a. Bonding arises from the overlap of atomic orbitals, combining to form molecular orbitals, whose clouds surround two or more atomic nuclei. b. The number of molecular orbitals is equal to the number of contributing atomic orbitals. c. In a molecular orbital (MO) diagram, the orbitals are filled up with available electrons (consistent with Pauli exclusion principle and Hunds rules), filling orbitals with lowest energy first. d. Types of molecular orbitals : overlap where centers of electron density are on the axis common to the two nuclei ( C symmetry = infinite fold rotation axis) : sideways overlap with C2 symmetry ( 2-fold rotation axis) and mirror plane

2. Qualitative Molecular Orbital Approach a. Total number of MOs is equal to total number of contributing AOs in the basis set (s, p, d). Usually neglect the low-lying 1s electrons for organic molecules. One could use hybrid AOs, and would ultimately get the same solution. For delocalized approach, it is easier to use pure AOs; for symmetry approach, it is easier to use hybrid AOs. b. Symmetry of MOs must conform to the symmetry of the molecule (all MOs must be either symmetric or antisymmetric to all symmetry elements). c. Orthogonal AOs do not interact.

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CHEM 6320

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d. Relative energy of AOs (and thus the derived MOs) goes down as the atom electronegativity increases. e. Relative energies of MOs go up with increasing number of nodes (but nodes are less destabilizing than nodes). The lowest energy MO is always totally bonding between all nuclei. The highest energy MO is always totally antibonding between all nuclei. f. Bonding MOs assign larger coefficients to more electronegative atoms. Bonding MOs assign smaller coefficients to less electronegative atoms. Antibonding MOs have opposite behavior. 3. Two-Atom Molecular Orbital Diagram a. Used for diatomic molecules and for a localized bonding picture b. Two atomic orbitals (on different atoms) combine to form two (twoatom) molecular orbitals (one bonding with positive overlap and lower energy and one anti-bonding with node and higher energy).
*MO = A B E A
atom A

B
atom B

MO = A + B

c. The interaction energy increases as extend of overlap increases (sigma > pi) as energies of the contributing atomic orbitals become more similar

strong interaction

weak interaction

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CHEM 6320

Fall 2005

4. Molecular Orbital Diagram for Carbon Monoxide

2p (C)

x* x *

y* y

2p (O)

2s (C)

* 2s (O)

a. Atomic orbitals of O are lower in energy than those of C. b. Molecular orbitals have different contributions from C and O atomic orbitals. 5. Delocalized Bonding a. For delocalized bonding (MOs represent more than two nuclei), general mathematical treatment of MOs as linear combination of atomic orbitals (LCAO) with appropriate weighing factors: = c11 + c2 2 + c33 + ... Note similarity to VB theory equation. In practice, both approaches give similar results, though VB calculations are more cumbersome. b. Electron density at each atom for any given molecular orbital One needs the overall sum of the square of the atom coefficients for all MOs containing electrons. The electron density at atom r is given by:
qr = n j c 2 jr
j

where j is the number of MOs, n is the number of electrons in that orbital, and c jr is the coefficient of AO in jth MO. n = 2 if the molecular orbital is doubly occupied n = 1 if the molecular orbital is singly occupied n = 0 if the molecular orbital is empty
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CHEM 6320

Fall 2005

6. Molecular Orbital Diagram for Methane a. Calculated MO energy (in a.u.) diagram for methane
+0.6887 +0.6441 0.5418 0.9320

11.2714

Photoelectron spectroscopy shows indeed two different ionization energies for methane. b. Consider methane in a cubic frame of reference (above) c. Atomic orbitals of carbon

d. Molecular orbitals of methane

e. Observations The MO involving 2s orbital of C has no node. The MOs involving 2p orbitals of C have one node. The MO involving 2s orbital of C is totally symmetric. The MOs involving 2p orbitals of C show C2 axis of symmetry. The antibonding MOs are similar but with opposite signs in the overlap region.
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CHEM 6320

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z
H H

7. Molecular Orbital Diagram for Ethylene a. MO energy (in a.u.) diagram for ethylene
D F, 4 H G C +0.89 +0.84 +0.63 +0.62 +0.59 +0.24 0.37 0.51 0.56 0.64 0.78 1.0
C 2pz

y
C C

H H

*
B E, 3 A

2 1

C 2pz

b. Ethylene molecular orbitals

c.

A B C D Observations 1-4 involves the 2s orbitals, E-H involves the 2px orbitals, A-D involves the 2py orbitals, and -* involves the 2pz orbitals of C.
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CHEM 6320

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3 and E orbitals are not orthogonal to each other. (They have the same symmetry.) A combination of 3 and E is a better description of the real orbital. Same for 4 and F orbitals.

3+E

The energy difference between bonding and antibonding MOs is smaller than that for the orbitals due to a weaker interaction (overlap) compared to . The orbitals and the nodes have some symmetry elements as the whole molecule. 8. Symmetry Approach to the Construction of Molecular Orbitals a. An equivalent approach to construction of delocalized (polyatomic) molecular orbitals considers these as a linear combination of localized (2-atom) molecular orbitals using molecular symmetry. b. Procedure Create a bonding model of localized MO from a basis set of AO Identify the symmetry elements of the molecule Identify which MOs might already be symmetry adapted For those which are not, group together orbitals which are transformed into each other by symmetry operations, and form + and combinations. The total number of orbitals at the end must equal that at the start. c. Observations All symmetry elements may not be needed, but conclusions can be based only on those symmetry elements to which the orbitals are adapted.

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CHEM 6320

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The situation becomes more complicated if there is a 3-fold or higher rotational axis. d. The example of water v' C2 3 Lewis structure predicts sp hybridization, v two of which are used for bonding and O * antibonding with two H 1s and the H H other two contain lone pairs. The elements of symmetry for water: There are two localized molecular orbitals:
O H H

O H H

The localized molecular orbitals transform into themselves by reflection in . Neither is symmetry adapted with respect to or C2. (For these symmetry operations, they are transformed into each other.) Therefore, take positive and negative combinations of these localized molecular orbitals to obtain:
O H H

O H H

S = 1 + 2

A = 1 2

Both new orbitals are either symmetric or antisymmetric to all symmetry elements. e. The example of methane
H H C H H

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CHEM 6320

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The four localized molecular orbitals:


H H C H
1

H H C
H C

H
H C

H
2

H
3

H
4

Note that: 1 (read transform into) 3 by C2(x); 1 2 by C2(y); 1 4 by C2(z) Delocalized molecular orbitals: S = 1 + 2 + 3 + 4 A xz = 1 + 2 3 4
H H C H
S

H H C

H
Axz

A yz and A xy are similar.

Final picture of the molecular orbital energy diagram is similar to the one before:

A S

Molecular orbitals as combination of atomic orbitals (from before):

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CHEM 6320

Fall 2005

9. Approximate LCAO-MO Theory a. Writing a molecular orbital as a linear combination of atomic orbitals (LCAO) leads to secular determinant. Molecular orbitals:

i = cis s
s =1

for n basis set atomic orbitals . (cis is the coefficient of atomic orbital s in ith molecular orbital.) Introduce in Schrdinger equation:
H i = cis H s = Ei i = Ei cis s
s =1 s =1 n n

Recall orthogonality and normalization requirements, which can be combined into one by saying that eigenfunctions constitute an orthonormal set: r s d = S rs (Srs = 0 if r s, Srs = 1 if r = s) Multiply Schrdinger equation above by i and integrate:
r =1s =1

c jr cis r H s d = E c jr cis r s d
r =1s =1

n n

n n

Abbreviate H rs = r H s d (called Coulomb integral) and S rs = r s d (called overlap integral).

Rewriting: E = r =1s =1 n n

c jr cis H rs
r =1s =1

n n

c jr cis S rs

The set of orbitals and energies are obtained by putting the condition that energy is minimum with respect to the coefficients (Variational Principle), i.e., the derivative of the energy with respect to the coefficients is zero. These conditions led to a set of n equations with n unknowns, cis.

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CHEM 6320

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These equations are called secular equations, and, written out, they are:
( H11 Ei S11 )ci1 + ( H 21 Ei S 21 )ci1 + M ( H n1 Ei S n1 )ci1 ( H12 Ei S12 )ci 2 ( H 22 Ei S 22 )ci 2 M + ... + ( H1n Ei S1n )cin + ... + ( H 2 n Ei S 2 n )cin M =0 =0 M =0

+ ( H n 2 Ei S n 2 )ci 2

+ ... + ( H nn Ei S nn )cin

These secular equations have non-trivial solutions if and only if the determinant of coefficients (called the secular determinant) is equal to zero: H11 Ei S11 H12 Ei S12 ... H1n Ei S1n H 21 Ei S 21 H 22 Ei S 22 ... H 2n Ei S 2 n =0 ... ... ... ... H n1 Ei S n1 H n 2 Ei S n 2 ... H nn Ei S nn When expanded, this represents an nth order polynomial in E, with n roots Ei. b. Electron correlation The determinant above cannot be solved exactly because of our ability to calculate the repulsion (interaction) terms Hrs. This is due to an obstacle known as electron correlation. For example, consider adding an electron to a system of one electron. The motion of the electron is influenced by its location relative to the first electron. But the location of the first electron is now dependent on the location of the second electron, which is exactly the problem we are trying to solve.

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