11/25/23, 8:30 PM LCAO model - Open Solid State Notes

When we consider an atom with multiple electrons, we need to determine which orbitals are
filled and which are not. We can predict the order of orbital filling using several rules:

Aufbau principle: electrons first fill a complete shell (all electrons with the same n) before
going to the next one

Madelung's rule: electrons first occupy the shells with the lowest n + l. If there are several
orbitals with equal n + l, electrons occupy those with smaller n

Combining the two rules, we obtain the shell filling order: 1s, 2s, 2p, 3s, 3p, 4s, 3d, etc.

While these rules accurately predict the electronic structure of most elements, they are only
approximate, and fail to describe some of the heavier elements.

Shell filling is important to us because the valence electrons (those in the outermost shell) are
the only ones participating in chemical reactions and electric conduction. From the valence
electrons' point of view, the inner shell electrons act like a negatively charged cloud. The
electrostatic repulsion between them reduces the effective charge of the atomic nucleus, but
does not play any further role.

Covalent bonds and linear combination of atomic orbitals

(LCAO)
A two-atom molecule

Consider two atoms next to each other, forming a diatomic molecule. The Hamiltonian
describing the energy of an electron on the molecule is

^ = V
H ^ + V
^ + K,
^
1 2

with V^ the potential energy due to the first nucleus, V^ due to the second nucleus, and K
1 2
^ the

kinetic energy of the electron.

Since the different orbitals of an atom are separated in energy, we consider only one orbital per
atom (even though this is often a bad starting point and it should only work for s-orbitals).

Additionally, we assume that the atoms are sufficiently far apart, such that the shape of the
orbitals barely changes due to the presence of the other atom.

If the atoms are far apart from each other such that they do not interact, the eigenstates of the
electrons are the atomic orbitals. If we call the atomic orbital of the electron on the first atom
|1⟩ and that of the electron on the second atom |2⟩, we have:

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^ ^
(V 1 + K)|1⟩ = ε 0 |1⟩,

^ ^
(V 2 + K)|2⟩ = ε 0 |2⟩.

Key idea: to find the wavefunction of the electron on the molecule - the molecular orbital -, we
search for a solution that is a linear combination of the atomic orbitals (LCAO):

|ψ⟩ = ϕ 1 |1⟩ + ϕ 2 |2⟩.

where ϕ and ϕ are probability amplitudes. The orbital |ψ⟩ is called a molecular orbital
1 2

because it describes the eigenstate of an electron on the diatomic molecule.

For simplicity, we assume that the atomic orbitals are orthogonal 1, i.e. ⟨1|2⟩ . This
= 0

orthogonality ensures that |ψ⟩ is normalized whenever |ϕ 1|

2
+ |ϕ 2 |
2
.
= 1

To find the possible values of ϕ and ϕ and the associated eigenenergies of the molecular
1 2

orbitals, we apply the full Hamiltonian to |ψ⟩:

H |ψ⟩ = E|ψ⟩ = ϕ 1 H |1⟩ + ϕ 2 H |2⟩.

Taking the left inner product with ⟨1|, we obtain

^ ^
⟨1|E|ψ⟩ = ϕ 1 ⟨1|H |1⟩ + ϕ 2 ⟨1|H |2⟩ = Eϕ 1 .

Similarly, taking the inner product with ⟨2| yields:

^ ^
Eϕ 2 = ϕ 1 ⟨2|H |1⟩ + ϕ 2 ⟨2|H |2⟩.

We combine these two equations into an eigenvalue problem:

^ ^
ϕ1 ⟨1|H |1⟩ ⟨1|H |2⟩ ϕ1
E( ) = ( )( ).
ϕ2 ^ ^ ϕ2
⟨2|H |1⟩ ⟨2|H |2⟩

The eigenvalue problem depends on only two parameters: the onsite energy
^ ^
⟨1|H |1⟩ = ⟨2|H |2⟩ ≡ E 0 that gives the energy of an electron occupying either of the atomic
orbitals, and the hopping integral (or just hopping) ⟨1|H
^
|2⟩ ≡ −t that characterizes the energy
associated with the electron moving between the two orbitals.

First, let us examine what constitutes the onsite energy and the hopping:

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^ ^ ^ ^ ^
E 0 = ⟨1|H |1⟩ = ⟨1|V 1 + V 2 + K|1⟩ = ε 0 + ⟨1|V 2 |1⟩,

where we used that (V^ 1

^
+ K)|1⟩ = ε 0 |1⟩ . In other words, the onsite energy is the combination
of the energy of the original orbital plus the energy shift ⟨1|V^ 2
|1⟩ of the electron due to the
potential of the neighboring atom. Second, the hopping is given by:

^ ^ ^ ^ ^
t = −⟨1|H |2⟩ = −⟨1|V 1 + V 2 + K|2⟩ = −⟨1|V 1 |2⟩.

The orbitals |n⟩ are purely real because we consider bound state solutions of the Schrödinger
equation. Hence t is real as well.

The eigenvalue problem we obtained describes a particle with a discrete 2×2 Hamiltonian:

E0 −t
H = ( ).
−t E0

Diagonalizing this LCAO Hamiltonian yields the following two eigenvalues:

E ± = E 0 ∓ t.

The eigenvector corresponding to the eigenvalue E +

= E0 − t is even and symmetric:

1
|ψ + ⟩ = (|1⟩ + |2⟩),
√2

while the eigenvector with energy E −

= E0 + t

1
|ψ − ⟩ = (|1⟩ − |2⟩)
√2

is odd/antisymmetric.

The molecular orbitals are shown in the figure below. According to the node theorem of
quantum mechanics, wave functions with lower energies have fewer points where ψ = 0 .
Because ψ −
= 0 between the two atoms, and ψ is not, we conclude that E
+ +
< E− , and
therefore t > 0 .

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11/25/23, 8:30 PM LCAO model - Open Solid State Notes

Bonding and antibonding orbitals

If we decrease the interatomic distance, the two atoms get closer and their atomic orbitals
start to overlap more. This increase in orbital overlap increases the hopping t. We plot the
symmetric and anti-symmetric energies as a function of the inter-atomic distance:

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