CHEM6085: Density Functional Theory

Lecture 3

Electronic wavefunctions and electronic density

C.-K. Skylaris

CHEM6085 Density Functional Theory 1

 The Born-Oppenheimer approximation
• Nuclei are much heavier than electrons and move at much slower speeds
• For example, the nuclei in H2 move only about 1pm for each 1000pm of
electronic motion
• To a very good approximation, we can assume that the electronic motions
are instantaneously “equilibrated” at each nuclear position

Atomic
Example: Vibration of diatomic molecule: electrons nucleus

Wrong picture: “electron cloud”

trails behind moving nuclei

Correct picture: “electron cloud”

instantaneously re-arranges itself
around moving nuclei

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 Born-Oppenheimer approximation
For a molecule, the wavefunction is a function of the coordinates of all
the electrons and all the nuclei:

• The Born-Oppenheimer approximation is based on the fact that nuclei

have much larger masses than the electrons
• To a good approximation, one can solve the Schrödinger equation only for
the electrons and assume the nuclei are frozen
• We will use this approximation from now on
• As a result, our wavefunctions will be functions only of electronic
coordinates:

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 The Born-Oppenheimer approximation
• In the Born-Oppenheimer approximation the nuclei are held fixed at given
locations and we solve the Schrödinger equation for the wavefunction of the
electrons alone
• The resulting molecular electronic energy depends on the nuclear coordinates
• For a diatomic we obtain the molecular potential energy curve
• For a polyatomic molecule we obtain the potential energy surface
Example: Potential energy curve of a diatomic

Equilibrium geometry de
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 Hamiltonian operator for water molecule
Water contains 10 electrons and 3 nuclei. We will use the symbols “O” for the oxygen (atomic number
ZO=8) nucleus, “H1” and “H2” (atomic numbers ZH1=1 and ZH2=1) for the hydrogen nuclei.
B.O. B.O. B.O.

Kinetic Kinetic Kinetic Kinetic energy

energy of energy of energy of of electron i
O H1 H2

Electron Electron Electron

attraction attraction attraction
to O to H1 to H2
E.g. Assume
Z1 =ZO
Z2=ZH1
Z3=ZH2
Electron-electron nucleus-nucleus
repulsion repulsion

• Quite a complicated expression! Hamiltonians for molecules become intractable

• Fortunately, we do not need to write all this for every molecule we study. We can develop general,
much more compact expressions that apply to any molecule, irrespective of its size

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 Example: Nuclear attraction potential for one O and two H

H2O OH + H

• How does the Hamiltonian

operator differ between these
examples?

• Can you suggest how you may

model the reaction OH+H  H2O
O + H2

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 Electronic wavefunctions
• Solutions (eigenfunctions) of the electronic Schrödinger equation
(i.e. under the Born-Oppenheimer approximation)
• Electronic wavefunctions, whether exact or approximate, must
have the following properties:
• Be finite
• Be continuous
• Be single valued
• Respect the indistinguishability of electrons
• Their square modulus is a probability distribution
• They must be antisymmetric

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 Continuous

good bad

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 Single valued

good bad

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 Spin
• Each electron has a “spin”, an intrinsic property which has the characteristics
of rotational motion, and is quantised
• Electronic spin is described by a spin angular momentum quantum number
s=½, and its z-component ms = ½ (“up” spin) or -½ (“down” spin)
• We represent the two spin states of the electron by two spin wavefunctions
and which are orthonormal:

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 Spatial and spin coordinates

• To describe the spin of an electron we include an extra “spin-coordinate”

• Therefore, for electron we have not only its three spatial coordinates
x,y,z (=r) but also by its spin coordinate
• We will denote these four coordinates collectively by x

• Particles whose spin quantum number s is a half-integer (e.g. 1/2, 3/2,

5/2, etc ) are called Fermions.
• Electrons and protons are examples of Fermions
• Particles whose spin quantum number s is an integer (e.g. 1, 2, 3) are
called Bosons. Photons are examples of Bosons

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 Antisymmetry of electronic wavefunctions
•Wavefunctions of Fermions change sign when the coordinates (space and
spin) of any two particles are exchanged.
•This property is called antisymmetry:

•Electrons are Fermions, therefore electronic wavefunctions must be

antisymmetric
•We need to include antisymmetry in all approximate wavefunctions we
construct

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 Spin needs to be taken into account in all expressions
Examples (with normalised wavefunctions):

Electronic density

Electronic kinetic energy

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 Electronic density vs electronic wavefunction

• The quantum theory is developed in terms of the wavefunction, which is a

function of 4xNel variables

• The electronic density is much simpler: It is a function of only 3

variables and has direct experimental relevance (e.g. Can be observed
by X-ray diffraction)

(Worked example: lets examine how this expression is derived)

• However the Schrödinger equation involves the wavefunction, not the

density

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 Example: Electronic density of a dipeptide (Ala-Gly)
Isovalue surfaces

n(r)=3.0 e/a03 n(r)=0.75 e/a03

n(r)=1.5 e/a03 n(r)=0.3 e/a03

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 What can we learn from the density

Example: Density of HeH+

• The positions of the

nuclei (cusps of the
density)
• Their atomic numbers
(from the slope of the
density near the nuclei)
• The total number of
electrons

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 In principle, you can obtain the energy from the density,
but only indirectly
Solve Schrödinger equation
Hamiltonian Wavefunction

Obtain
number of Calculate energy
electrons, and other
atomic experimental
numbers, observables from
atomic wavefunction
positions

Density Energy
Is there a way to go from the density
directly to the energy without having
to solve the Schrödinger equation?

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 Homework

1) For the He atom the wavefunction is approximated in terms of 1s atomic orbitals, one occupied by an up spin
electron and one occupied by a down spin electron. Which if the following possible wavefunctions is antisymmetric
(note that we are using a shorthand notation where “1” means the spin and space coordinates of electron 1, etc):

2) The term “external potential” is often used to refer to the potential energy operator for attraction of the electrons
to the nuclei. For example, the external potential of a HeH ion is . Write
down

an expression for the external potential of the Hamiltonian operator for the water molecule from slide 5.

3) Taking into account the indistinguishability of electrons, show how the external potential energy (see previous
question)

can be equivalently written as which is an expression involving the density instead of the
wavefunction.

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 5-minute quiz
Name : Date :
Surname:

1) Which of the following types of information do we need in order to write down the electronic Hamiltonian
operator for a molecule ?
a) The position of each nucleus
b) The atomic number of each nucleus
c) The mass of each nucleus
d) The spin of each nucleus
e) The total number of electrons

2) Which of the above can be obtained by examination of the electronic density and how?

3) For the He atom the wavefunction is approximated as a product of 1s atomic orbitals, one occupied by an up
spin electron and one occupied by a down spin electron as . Find an expression for
the electronic density given that the atomic orbitals obtain the following condition (normalisation):

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