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What is the molecule?

NH3

What is the calculation method?

RB3LYP

6-31G(d,p)

What is the final energy E(RB3LYP) in atomic units (au)?

-56.55776873

What is the RMS gradient (au)?

0.00000485

What is the point group of your molecule?

C3V

Optimised Bond Length (Å):

1.01798

Optimised Bond Angle:

105.741

Optimisation Data:


 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

Jmol Image:

NH3

Optimised NH3 on Gauss

here

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

6

Which modes are degenerate (ie have the same energy)?

2,3;5,6

Which modes are "bending" vibrations and which are "bond stretch" vibrations?

Bending Modes = 1,2,3

Stretching = 4,5,6

Which mode is highly symmetric?

4

One mode is known as the "umbrella" mode, which one is this?

1

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

4

Charge for N = -1.125

Charge for H = 0.375

This is expected because nitrogen is more electronegative than hydrogen, hence I expect nitrogen to be negative and hydrogen to be positive.

N2 Molecule

The summary information

What is the molecule?

N2

What is the calculation method?

RB3LYP

What is the basis set?

6-31G(d,p)

What is the final energy E(RB3LYP) in atomic units (au)?

-109.52412868

What is the RMS gradient (au)?

0.00000060

What is the point group of your molecule?

D*H

Optimised Bond Length (Å):

1.10550

Optimised Bond Angle:

180

Optimisation Data:

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

List the frequencies and confirm that there are no negative frequencies:

2457.33 cm-1, hence there are no negative frequencies.

N2 Optimisation on Gauss

Jmol Image:


H2 Molecule

The summary information

What is the molecule?

H2

What is the calculation method?

RB3LYP

What is the basis set?

6-31G(d,p)

What is the final energy E(RB3LYP) in atomic units (au)?

-1.17853936

What is the RMS gradient (au)?

0.00000017

What is the point group of your molecule?

D*H

Optimised Bond Length (Å):

0.74279

Optimised Bond Angle:

180

Optimisation Data:

 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

List the frequencies and confirm that there are no negative frequencies:

4465.68 cm-1, hence there are no negative frequencies.

H2 Optimisation on Gauss

Jmol Image:


Energy Calculations of Reaction

E(NH3)= -56.55776873

2*E(NH3)= -113.11553746

E(N2)= -109.52412868

E(H2)= -1.17853936

3*E(H2)= -3.53561808

ΔE = 2*E(NH3)-[E(N2)+3*E(H2)]= -113.11553746-[-109.52412868 + -3.53561808] = -0.0557907 au = -146.47848285 KJ mol-1

As the energy is negative, the reaction must be exothermic which suggests the product NH3 is more stable than the reactants H2 and N2.

O2 Molecule

Data

What is the molecule?

O2

What is the calculation method?

RB3LYP

What is the basis set?

6-31G(d,p)

What is the final energy E(RB3LYP) in atomic units (au)?

-150.25742434

What is the RMS gradient (au)?

0.00007502

What is the point group of your molecule?

D*H

Optimised Bond Length (Å):

1.21602

Optimised Bond Angle:

180°

Optimisation Data:

 Item               Value     Threshold  Converged?
 Maximum Force            0.000130     0.000450     YES
 RMS     Force            0.000130     0.000300     YES
 Maximum Displacement     0.000080     0.001800     YES
 RMS     Displacement     0.000113     0.001200     YES

Jmol Image:

O2

Optimised O2 on Gauss

Vibrational modes of O2

There is one mode at 1642.74 cm-1 which would be expected according to 3N-5 rule.

There are no charges because the molecule only contains one element, its a diatomic.

Molecular Orbitals of O2

u

1πu Orbital of O2 on Gauss

Energy: - 0.50754

Contributing AOs: two 2px or two 2pz

Contributes to Oxygen bond

Is the MO occupied or unoccupied: Occupied with a pair of electrons

g

3σg Orbital of O2 on Gauss

Energy: - 0.53151

Contributing AOs: two 2pz

Is the MO occupied or unoccupied: Occupied with a pair of electrons

g*

1πg* Orbital of O2 on Gauss

Energy: - 0.17928

Contributing AOs: 2px and 2py

Is the MO occupied or unoccupied: Unoccupied

This is the LUMO

u*

3σu* Orbital of O2 on Gauss

Energy: - 0.79821

Contributing AOs: Two 2pz

Is the MO occupied or unoccupied: Occupied with a pair of electrons electrons

g

2σg Orbital of O2 on Gauss

Energy: - 1.27663

Contributing AOs: Two 2s

Is the MO occupied or unoccupied: Occupied with a pair of electrons