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NH3 molecule

Optimisation of the molecule

Molecule name: NH3

Calculation method: RB3LYP

Basis set: 6-31G(d.p)

Final energy E(RB3LYP): -56.55776873au

RMS gradient: 0.00000485au

Point group: C3V

Bond distance: 1.01798

Bond angle: 105.741

         Item               Value     Threshold  Converged?
 Maximum Force            0.000004     0.000450     YES
 RMS     Force            0.000004     0.000300     YES
 Maximum Displacement     0.000072     0.001800     YES
 RMS     Displacement     0.000035     0.001200     YES
test molecule

The optimisation file is linked to here.


Vibrations of the molecule

1. How many modes do you expect from the 3N-6 rule? 6

2. Which modes are degenerate (ie have the same energy)? Mode #5 and #6

3. Which modes are "bending" vibrations and which are "bond stretch" vibrations? Bending: #1,2,3 ; Stretching: #4,5,6

4. Which mode is highly symmetric? Mode #4

5. One mode is known as the "umbrella" mode, which one is this? Mode #1

6. How many bands would you expect to see in an experimental spectrum of gaseous ammonia? 3


Charge analysis

Charge on the N-atom: -1.125

Charge on the H-atoms: 0.375

A negative and positive charge of the N-atom and H-atom is expected respectively. This is because nitrogen is more electronegative than hydrogen.


H2 molecule

Optimisation of the molecule

Molecule name: H2

Calculation method: RB3LYP

Basis set: 6-31G(d.p)

Final energy E(RB3LYP): -1.17853936au

RMS gradient: 0.00000017au

Point group: C1

Bond distance: 0.74279

        Item               Value     Threshold  Converged?
 Maximum Force            0.000000     0.000450     YES
 RMS     Force            0.000000     0.000300     YES
 Maximum Displacement     0.000000     0.001800     YES
 RMS     Displacement     0.000001     0.001200     YES
test molecule

The optimisation file is linked to here.


Vibrations of the molecule

Frequency: 4465.68


N2 molecule

Optimisation of the molecule

Molecule name: N2

Calculation method: RB3LYP

Basis set: 6-31G(d.p)

Final energy E(RB3LYP): -109.52412868au

RMS gradient: 0.00000060au

Point group: C1

Bond distance: 1.10550

         Item               Value     Threshold  Converged?
 Maximum Force            0.000001     0.000450     YES
 RMS     Force            0.000001     0.000300     YES
 Maximum Displacement     0.000000     0.001800     YES
 RMS     Displacement     0.000000     0.001200     YES
test molecule

The optimisation file is linked to here.


Vibrations of the molecule

Frequency: 2457.33



Reaction energies

E(NH3)= -56.55776873au

2*E(NH3)= -113.1155375au

E(N2)= -109.52412868au

E(H2)= -1.17853936au

3*E(H2)= -3.53561808au

ΔE=2*E(NH3)-[E(N2)+3*E(H2)]= -0.05579074au = -146.4785879kJ/mol

The ammonia product is more stable because the energy required for conversion is negative, i.e. the energy of the ammonia product is lower than the total energy of the gaseous reactants.


Project molecule: F2

Optimisation of the molecule

Molecule name: F2

Calculation method: RB3LYP

Basis set: 6-31G(d.p)

Final energy E(RB3LYP): -199.49825218au

RMS gradient: 0.00007365au

Point group: C1

Bond distance: 1.40281

         Item               Value     Threshold  Converged?
 Maximum Force            0.000128     0.000450     YES
 RMS     Force            0.000128     0.000300     YES
 Maximum Displacement     0.000156     0.001800     YES
 RMS     Displacement     0.000221     0.001200     YES
test molecule

The optimisation file is linked to here.


Vibrations of the molecule

Frequency: 1065.09


Charge analysis

There is no charge within the molecule because both of the atoms are F-atoms and there is no electronegativity difference between them.


Molecular orbitals

This is the first MOs, formed from the two 1s AOs of the F-atoms. The energy level is -24.79730au, which is much deeper comparing to the later MOs which are formed by the valence shell AOs. It can be seen that the orbitals is hardly overlapping, stating how it is not very involved in the chemical bonding between the F-atoms.

Moving on to the σ2s bonding orbital, which are formed from the 2s AOs of the F-atoms. The highly overlapping orbitals are almost shown as one surface only. They are of a much higher energy than the first two MOs where the energy level is -1.33659au. As these are formed from the valence shell AOs, they are highly involved in the chemical bonding.

The above 2 images shows the two σ2pz bonding and anti-bonding orbitals. The energy levels are -0.58753au and -0.12679au respectively. They are formed from the 2p orbitals of the F-atoms which lie along the same orientation as the F-F bond. Thus, it is a sigma MO. Due to the large energy gap between the 2s and 2p AOs, there is no mixing between the 2s and 2p orbitals and thus, the MOs do not give a distorted shape like those in N2. As the bonding orbital is occupied while the anti-bonding orbital is empty, these 2 electrons in the bonding orbital are the bonding electrons in F2.

The above 2 images shows the two π2p bonding and anti-bonding orbitals. The energy levels are -0.52332au and -0.39190au respectively. There are another 2 degenerate MOs because they are all formed from the 2px and 2py AOs of the F-atoms. They are perpendicular to the F-F bond and are called as pi MOs. As they are both occupied, the electrons in these MOs act as the non-bonding electrons. As a result, the fluorine molecule is only single bonded, which is contributed by the bonding electrons in the σ2pz bonding orbitals.