MOLECULAR

PHYSICS
Part IV
Prepared by Catherine Paschal
Mwenge Catholic University

Catherine Paschal @MWECAU 1

Molecular Orbital Method
MO Treatment of Hydrogen Molecule
• The treatment of hydrogen molecule in MO theory is
essentially the same as that of H!" molecule.
• The Hamiltonian operator for H! molecule is:
ℏ! ! 𝑘𝑒 ! 𝑘𝑒 !
𝐻= − 𝛻# − − +
2𝑚 𝑟$# 𝑟%#
ℏ! ! 𝑘𝑒 ! 𝑘𝑒 ! 𝑘𝑒 ! 𝑘𝑒 !
− 𝛻! − − + +
2𝑚 𝑟%! 𝑟$! 𝑟#! 𝑅
where 1 and 2 represent electrons and 𝑎 and 𝑏 protons
(Figure 5).

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Molecular Orbital Method

Figure 5: Inter particle distances in hydrogen molecule.

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Molecular Orbital Method
• Writing,
ℏ! ! 𝑘𝑒 ! 𝑘𝑒 !
𝐻(1) = − 𝛻" − −
2𝑚 𝑟#" 𝑟$"
ℏ! ! 𝑘𝑒 ! 𝑘𝑒 !
𝐻(2) = − 𝛻! − −
2𝑚 𝑟#! 𝑟$!
𝑘𝑒 ! 𝑘𝑒 ! 𝑘𝑒 ! 𝑘𝑒 !
𝐻 = 𝐻(1) + + 𝐻(2) + + −
𝑅 𝑅 𝑟"! 𝑅
• We shall compute the expectation value of 𝐻 with a trial
wavefunction.
• As the term −𝑘𝑒 !/𝑅 is independent of electronic coordinates, it
makes no difference to electronic wavefunction whether it is
retained in the Hamiltonian or incorporated later in the energy
expression as an additional term −𝑘𝑒 !/𝑅.

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Molecular Orbital Method
• The Hamiltonian inside the brackets in Eq. (28) is the same as
the one solved for H! " molecule.
• Therefore, one can reasonably take that in the ground state of
hydrogen molecule both the electrons occupy the bonding
orbital 𝜓# of H!" which is symmetric with respect to the
interchange of nuclei 𝑎 and 𝑏.
• The trial wavefunction for the hydrogen molecule can then be
written as:
𝜓& (1) + 𝜓' (1) 𝜓& (2) + 𝜓' (2)
𝜓$% = 𝜓# (1)𝜓# (2) = ⋅
2 + 2𝑆 2 + 2𝑆
1
= 𝜓& (1) + 𝜓' (1) 𝜓& (2) + 𝜓' (2)
2(1 + 𝑆)

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Molecular Orbital Method
• We now include the electron spin and Pauli's principle
into the formalism.
• Spin functions for the two electron system are given in
Tables:
𝛼(1)𝛼(2)
#
• Symmetric: [𝛼(1)𝛽(2) + 𝛽(1)𝛼(2)]
!
𝛽(1)𝛽(2)
#
• Antisymmetric: [𝛼(1)𝛽(2) − 𝛽(1)𝛼(2)]
!

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Molecular Orbital Method
• 𝛼 (1) means the first electron is in a ‘spin up’ state, 𝛽 (1) means the first
electron is in a ‘spin down’ state and so on.
• According to Pauli's principle, the total wavefunction must be
antisymmetric with respect to the interchange of the two electrons.
• Therefore, the symmetric 𝜓!" (Eq. 29) has to combine with the
antisymmetric spin part leading to the wavefunction:
1 1
𝜓# (1) + 𝜓$ (1) 𝜓# (2) + 𝜓$ (2) [𝛼 (1) 𝛽(2) − 𝛽(1)𝛼(2)]
2(1 + 𝑆) 2
• This is a singlet state as its spin 𝑆 = 0.
• The energy is not affected by the inclusion of spin part as the
Hamiltonian does not contain spin terms.
• The space part, Eq. (29), can then be taken as the MO for the evaluation
of energy.
• With Eq. (29) as trial wavefunction,

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Molecular Orbital Method

𝑘𝑒 % 𝑘𝑒 %
𝜓!" |𝐻|𝜓!" = 𝜓!" 𝐻(1) + 𝜓!" + 𝜓!" 𝐻(2) + 𝜓!"
𝑅 𝑅
𝑘𝑒 % 𝑘𝑒 %
+ 𝜓!" 𝜓 − 𝜓!" 𝜓!"
𝑟&% !" 𝑅
𝑘𝑒 % 𝑘𝑒 %
𝐸 = 2𝐸& (𝑅) + 𝜓!" 𝜓!" −
𝑟&% 𝑅
where 𝐸& is the energy of the H%' molecule.
• Substituting the value of 𝐸& from Eq. (17.24), we get
2 𝑉## + 𝑉#$ 𝑘𝑒 % 𝑘𝑒 %
𝐸 = 2𝐸( − + + 𝜓!" 𝜓!"
1+𝑆 𝑅 𝑟&%

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Molecular Orbital Method
• After computing the contribution due to the electron-
electron repulsion, the total energy is minimized with
respect to the internuclear separation 𝑅.
• Coulson from a refined variational calculation obtained
𝑟& = 0.732Å for the equilibrium internuclear distance
and a dissociation energy 𝐷' = 3.49eV.
• The experimental values are 0.74Å and 4.75eV
respectively.
• The MO given in Eq. (29) may be written in the form:
1 𝜓$ (1)𝜓$ (2) + 𝜓% (1)𝜓% (2)
𝜓() =
2(1 + 𝑆) +𝜓$ (1)𝜓% (2) + 𝜓% (1)𝜓$(!)
Catherine Paschal @MWECAU 9
Molecular Orbital Method
• The first two terms correspond to the situation in which
both the electrons are associated with the same proton.
• These represent the ionic structures 𝐻$, 𝐻%" and
𝐻$" 𝐻%, respectively.
• However, the third and fourth terms represent the
situation in which the electrons are shared equally by
both the protons and hence they correspond to covalent
structures of the hydrogen molecule.
• The MO selected gives equal importance to ionic and
covalent structures which is probably causing the
disagreement with the experimental values.
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