Christopher Fitzpatrick B7

Results and Analysis

Infra-Red Data Analysis:

Figure 12: Graph for determination of B0

400.000 E / cm-1 300.000 200.000 100.000 0.000 0 2 4 J0 + 1/2 6 8 10 y = 39.218x + 1.6695 R = 1

Table 1 J0 + 1/2 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 E(B0) / cm-1 59.870 100.30 138.74 178.42 217.53 256.74 295.78 334.70

Table 2

Figure 13: Graph for determination of B1

400.000 E / cm-1 300.000 200.000 100.000 0.000 0 2 4 J0 + 1/2 6 y = 39.436x - 0.4687 R = 1 8 10

E(B1) / J0 + 1/2 cm-1 1.5 58.790 2.5 98.500 3.5 137.42 4.5 176.95 5.5 216.28 6.5 255.32 7.5 295.01 8.5 335.15 9.5 374.46

Graph of E against J0 + for B0 gives a gradient of 39.218 cm-1. Therefore B0 equals:

Christopher Fitzpatrick B7 Therefore equals: ( ( ) )

Graph of E against J0 + for B1 gives a gradient of 39.436cm-1. Therefore B1 equals:

Therefore,

equals: ( ( ) ) and : )

, the moment of inertia, equals the average of (

You can use the value of ( (

to calculate the bond angle of the N-H bond: ) )

( ( ( ) ) ( ( ( (

) ) ) )

Raman Data Analysis:

Sample B: Acetonitrile

Christopher Fitzpatrick B7 Structure =

Point group = C3V Nitrile Stretch = 2259.35cm-1 = 225935m-1 , where is the reduced mass of CN Therefore, ( ) ( )

The range of for a nitrile is given as 2260-2200cm-1. The value for obtained experimentally from acetonitrile falls within this range. This is because vibrations can be localised in a particular part of the molecule, where the force constant between two atoms in a chain is very different to the force constant from those between other atoms in the chain. The force constant of the C-N bond is very different to the force constant of the C-C bond, as the C-N bond is a triple bond, which will give a much higher force constant than the single C-C bond. Therefore, the vibrations in the range of 2260-2200cm-1 will be localised in the C-N region, effectively treating the C-N region as a diatomic. Sample E: cis-dichloroethene Structure =

Point Group = C2V

C2V A1 A2 B1 B2

E 1 1 1 1

C2 1 1 -1 -1

v (xz) 1 -1 1 -1

v (yz) 1 -1 -1 1

z Rz x, Ry y, Rx

x2, y2, z2 xy xz yz

Modes of vibration = 3N 6, where N is the number of atoms present. Therefore, modes of vibration equal: 3N 6 = 18 6 = 12.

Christopher Fitzpatrick B7 Reducible representation: C2V 3N E 18 C2 0 v (xz) 0 v (yz) 6

( ( ( (

) ) ) )

Raman and IR activity: Those vibrational modes with translational character will be IR active. In this case, all modes except for those with A2 symmetry have translational character, so will be IR active. Those vibrational modes with quadratic terms in the character table will be Raman active. In this case, all vibrational modes have quadratic terms, so all are Raman active. Sample F: trans-dichloroethene Structure =

Point Group = C2h C2h Ag Bg Au Bu E 1 1 1 1 C2 1 -1 1 -1 i 1 1 -1 -1 h 1 -1 -1 1 x2, z2, y2, xy xz, yz

Rz Rx, Ry z x, y

Modes of vibration = 3N 6 = 18 6 = 12

Christopher Fitzpatrick B7 Reducible Representation: C2h 3N E 18 C2 0 i 0 h 6

( ( ( (

) ) ) )

Raman and IR activity: Those vibrational modes with translational character will be IR active. In this case, the vibrational modes with Au and Bu symmetry have translational character, so will be IR active. Those vibrational modes with quadratic terms will be Raman active. In this case, the vibrational modes with Ag and Bg symmetry have quadratic terms, so will be Raman active. Spectra: Annotated IR and Raman spectra have been handed in attached. Those peaks which are unassignable in the Raman spectra will be caused by the first overtones of some vibrational modes, which are guaranteed to be Raman active in each case, as in cis-dichloroethene, all modes are Raman active, and in trans-dichloroethene, the Ag identity is Raman active, and any mode multiplied by itself will result in Ag symmetry.

Conclusion
Our main results were the moment of inertia for ammonia, obtained from IR data at several different pressures, which was equal to , and the bond angle of the N-H bonds in ammonia, obtained from the moment of inertia, which was equal to 65.2 . The main conclusion is that ammonia can undergo quantum tunnelling at high vibrational energy levels, causing splitting of its rotational IR spectra.

Christopher Fitzpatrick B7

Questions
Individual rotation lines have been identified on Figure 5, which is attached to this script. The splitting is caused by quantum mechanical tunnelling, which is the process by which energy barriers can be overcome by quantum particles, as shown below:

Via quantum mechanical tunnelling, NH3 reconfigures from its original trigonal pyramid structure into an inverted trigonal pyramid structure, via a planar intermediate. The two pyramid structures will have identical potential energy, and the planar intermediate will have a greater potential energy, due to the steric hindrance of the atoms being in the same plane, as shown below:

The magnitude of energy splitting is the difference between the potential energy wells, represented by 2a on the diagram above. The magnitude of the splitting is related to the time taken for the reconfiguration to occur

Christopher Fitzpatrick B7

Accreditation
1. http://en.wikipedia.org/wiki/File:Acetonitrile-2D.png structural image on page 3 of script. 2. http://en.wikipedia.org/wiki/1,2-Dichloroethene structural images on pages 3 and 4 of script. 3. http://www.princeton.edu/chemistry/macmillan/group-meetings/DEC_tunneling.pdf potential energy diagrams on page 6 of script.