Electronic Structure Models

Hckel Model (1933) Basic Assumptions: (a) One orbital per atom contributes to the basis set; all orbitals "equal"

(b) The relevant integrals involving the Hamiltonian are if = (same site) H = if but and are bonded (nearest neighbors) 0 otherwise

(c) The atomic orbitals are assumed normalized and orthogonal: S = 1 if = 0 if

and are parameters; their values will be adjusted to experimental data of some sort, typically after the calculation is done (or not at all)

Consider, as the easy (trivial?) example, ethylene with the 2p() orbitals as the basis set. The secular determinant for two basis functions is

H11 - ES11

H12 - ES12
A

=0 H21 - ES21 H22 - ES22

which, in the Hckel model, becomes -E =0 -E

Multiply out the secular determinant and find the roots: ( - E)2 - 2 = 0 => ( - E)2 = 2 => - E =

or

E2 = -

E1 = +
E1 = + and E2 = - We may then find the two sets of coefficients (one for 1, one for 2) from the secular equations

-E

c1

-E

c2

( - E) c1 + c2 = 0 c1 + ( - E) c2 = 0 When E = E1 = + , we find by insertion (into either equation) ( - ( + )) c1 + c2 = 0 => - c1 + c2 = 0 => - c1 = - c2 => c1 = c2 When E = E2 = - , we find ( - ( - )) c1' + c2' = 0 => c1' + c2' = 0 => c1' = - c2' => c1' = -c2'

The coefficients must, of course, be equal in magnitude, since the two carbon atoms are symmetry equivalent. So,

1 = c1 (1 + 2) 2 = c1' (1 - 2)

E1 = + E2 = -

The MO's should be properly normalized in order to represent probability distributions. The atomic orbitals 1 and 2 are assumed to be properly normalized,

V 1 1dV = V 2 2 dV = 1
and orthogonal

V 1 2dV = V 2 1 dV = 0
So we find the actual value for c1 or c1' from the normalization condition:

V 1 1 dV = 1 => V c12 (1 + 2)2 dV = 1 =>

c12V 1 1 dV + 2c12V 1 2 dV + c12V 2 2 dV = 1 => c12 + 2c12S12 + c12 = 1 => c1 = [2(1+ S12)]-1/2

Similarly:

V 2 2 dV = 1 => c1' = [2(1 - S12)] -1/2

Within the Hckel-model, S12 = 0 and we get c1 = (2)-1/2 and c1' = (2)-1/2. The overlap between the two pi-orbitals in ethylene is in fact near 0.25, and if there were no overlap between the orbitals, there would be no pi-bonding at all. Interatomic overlap is a prerequisite for covalent chemical bonding. Nevertheless, in most semi-empirical methods the overlap

integrals are neglected in normalization considerations, as a mathematical convenience. Thus, the normalized Hckel -MO's for ethylene are 1 = (2)-1/2 (1 + 2) 2 = (2)-1/2 (1 - 2)

E1 = + E2 = -

2 = (2)-1/2 (1 -

2)

E2 = -

E1 = + -1/2 (1 + 2) 1 = (2)

1 increases the electron density between the atoms relative to the two atoms non-interacting; 2 has depleted electron density between the atoms relative to the two atoms non-interacting. 1 is a "bonding" orbital, 2 is an "antibonding" orbital. Therefore, E1 is less than E2 and must be a negative quantity. = energy of an electron in orbital in the molecule (negative quantity). depends on orbital type and nuclear charge. = energy gained by electron "delocalization" or "resonance" between orbitals and . depends on orbital types, nuclear charges, and degree of overlap between the orbitals. Electronic energy: E = 2E1 = 2( + ) E(isolated atoms) = + = 2; Energy gained by bonding: 2

In fact, most useful results from Hckel calculations are expressed in terms of .

(1) Optical excitation; Plot HOMO-LUMO energy difference vs. UVmaximum for lowest allowed absorption band for a series of polyenes or rings.

E = E(LUMO) - E(HOMO) x x x x x x

x x

max
Optimal value of = -2.7 eV

(cm-1)

(2) Ionization potential; IP = -E(HOMO) Optimal value of = -2.9 eV

(3) Electron affinities; EA = E(LUMO) Optimal value of = -2.4 eV

(4) Delocalization energy; defined as E (delocalized) - E (localized), should correlate with heats of formation data. Optimal value of = -0.69 eV (!!!)

Conclusion: Different optimal parameters for different properties. The optimal parameters tend to cluster in two groups, one for "spectroscopic" properties and one for "thermodynamic" properties (dynamic vs. static). This observation and idea carries over to more elaborate electronic structure models as well --- a particular parameterization scheme works best for ground state properties whereas a (quite) different set of parameters are more appropriate for spectroscopic (excited state) properties

The pi molecular orbitals and energies for butadiene are attached. They are the results of diagonalizing a 4x4 determinant (1,2,3,4) within the Hckel model.

Useful indices: charges and bond orders -charge, i.e. number of pi-electrons per atom q = i Ni ci2

N = # electrons in MO i (2,1, or 0) ci = coefficient of atom in MO i Sum is over all occupied MO's

Ethylene: q1 = 2[(2)-1/2]2 = 1.00 = q2 Butadiene: q1 = 2 (0.37)2 + 2 (0.60)2 = 1.00 = q2 = q3 = q4 Bond order: The bond order between two (adjacent) atoms and is p = i Ni ci ci

Ni = # electrons in MO i (2,1, or 0) ci = coefficient on atom in MO i ci = coefficient on atom in MO i

Note: p = q

Ethylene: p12 = 2 (2)-1/2(2)-1/2 = 1.00 (standard)

Butadiene:

p12 = 2(0.37)(0.60) + 2(0.60)(0.37) = 0.89 p23 = 2(0.60)(0.60) + (0.37)(-0.37) = 0.45 p34 = 2(0.37)(0.60) + 2(0.60)(0.37) = 0.89

p12 < 1.00 and p23 > 0.45 => delocalization of pi-electron into the central bond

Pi bond-orders between adjacent atoms range from 0.0 to 1.0 (0.66 in benzene, for example). There is excellent correlation between pi bond orders and bond lengths. For example,

R(C1-C2) = 1.517 - 0.189 pc1-c2

The matrix P which has as its elements the charges (diagonal) and bond-orders (off-diagonal) is called the charge - bond order matrix. In fancier language, it is called the density matrix; in very fancy language, it is called the "first order reduced density matrix".

CALCULATION FOR ETHYLENE HUCKEL MATRIX BY COLUMNS 1 2 1 2 0 0.00000 1.00000 1.00000 0.00000 MO- 1 MO- 2 MO-

0 E/BETA C- 1 C- 2

1.00000 -1.00000

0.707107 -0.707107 0.707107 0.707107

ORBITAL OCCUPANCY MO 1--2 MO 2--0 MO 2.00000

HUCKEL ENERGY (UNITS OF BETA) = BOND-ORDER MATRIX BY COLUMNS 1 2 1 2 1.00000 1.00000 1.00000 1.00000 CHARGE DENSITY C C 1 2 1.00000 1.00000 NET CHARGE 0.00000 0.00000 SPIN DENSITY 0.00000 0.00000

SPIN DENSITY IS FOR HIGHEST MULTIPLICITY

CALCULATION FOR BUTADIENE HUCKEL MATRIX BY COLUMNS 0 1 2 1 2 3 4 0.00000 1.00000 0.00000 0.00000 1.00000 0.00000 1.00000 0.00000 K

3 4

0.00000 1.00000 0.00000 1.00000 0.00000 0.00000 1.00000 0.00000 MO- 1 MO- 2 MO- 3 MO- 4 1.61803 0.61803 -0.61803 -1.61803 MO-

0 0 E/BETA CCCC1 2 3 4

0.371748 0.601501 0.601501 0.371748 0.601501 0.371748 -0.371748 -0.601501 0.601501 -0.371748 -0.371748 0.601501 0.371748 -0.601501 0.601501 -0.371748

ORBITAL OCCUPANCY MO 1--2 MO 2--2 MO 3--0 MO 4--0 MO 4.47214

HUCKEL ENERGY (UNITS OF BETA) = BOND-ORDER MATRIX BY COLUMNS 1 2 3 4 1 2 3 4 1.00000 0.89443 0.00000 -0.44721 0.89443 1.00000 0.44721 0.00000 0.00000 0.44721 1.00000 0.89443 -0.44721 0.00000 0.89443 1.00000

CHARGE DENSITY C C C C 1 2 3 4 1.00000 1.00000 1.00000 1.00000

NET CHARGE 0.00000 0.00000 0.00000 0.00000

SPIN DENSITY 0.00000 0.00000 0.00000 0.00000

SPIN DENSITY IS FOR HIGHEST MULTIPLICITY