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Rep:Mod:lh1002

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BH3 molecule

Optimization summary

Item                     Value        Threshold    Converged?
Maximum Force            0.000009     0.000450     YES
RMS     Force            0.000006     0.000300     YES
Maximum Displacement     0.000034     0.001800     YES
RMS     Displacement     0.000022     0.001200     YES
Predicted change in Energy=-4.417971D-10
Low frequencies ---   -0.6727   -0.3834   -0.0054   12.9097 16.4795   16.4932
Low frequencies --- 1163.0392 1213.2115 1213.2142
vibration modes  frequency(cm-1)  Intensity     Symmetry      IR active?    Type
1                1163             93            A2"           yes           out-of-plane bend
2                1213             14            E'            slightly      bend
3                1213             14            E'            slightly      bend
4                2582             0             A1'           no            symmetric stretch               
5                2715             126           E'            yes           asymmetric stretch 
6                2715             126           E'            yes           asymmetric stretch 

Despite there are 6 vibration modes, only 3 peaks are observable. Because mode2 and mode3 as well as mode5 and mode6 have the same frequencies, their peaks coincide. Mode4 is IR active because its dipole moment can cancel out.

optimized BH3 molecule

The completed BH3 frequency *.log file is liked to here

This is the another link if you can't open the link above File:LH1002 BH3 FREQ.LOG

MO diagram

MO QUESTION:
1. Are there any significant differences between the real and LCAO MOs?
no
2. What does this say about the accuracy and usefulness of qualitative MO theory?
Quite high accuracy Since BH3 is made up by small atoms

Ng611 (talk) 23:30, 15 May 2018 (BST)What about the usefullnes of qMO theory? Are there any differences?

Association energies: Ammonia-Borane

NH3 information

optimized NH3 molecule

The completed BH3 frequency *.log file is liked to here

Item                     Value        Threshold    Converged?
Maximum Force            0.000006     0.000450     YES
RMS     Force            0.000003     0.000300     YES
Maximum Displacement     0.000013     0.001800     YES
RMS     Displacement     0.000007     0.001200     YES
Predicted change in Energy=-1.131567D-10
Low frequencies ---   -0.0138   -0.0032   -0.0015    7.0783    8.0932    8.0937
Low frequencies --- 1089.3840 1693.9368 1693.9368

Ammonia-Borane information

optimized NH3BH3 molecule

The completed BH3 frequency *.log file is liked to here

Item                     Value        Threshold    Converged?
Maximum Force            0.000208     0.000450     YES
RMS     Force            0.000056     0.000300     YES
Maximum Displacement     0.001051     0.001800     YES
RMS     Displacement     0.000430     0.001200     YES
Predicted change in Energy=-1.565485D-07
Low frequencies ---  -19.3099   -0.0315   -0.0057    0.0256    9.2849    9.2934
Low frequencies ---  262.4242  631.2240  637.8386

Ammonia-Borane association energy

E(NH3)= -56.55777 a.u.= -148464 kJ/mol
E(BH3)= -26.61532 a.u.= -69865 kJ/mol 
E(NH3BH3)= -83.22469 a.u.= -218465 kJ/mol
ΔE= E(NH3BH3)-[E(NH3)+E(BH3)] = -218465 -(-69865-148464)=-135 kJ/mol

Association energy is negative because this is the energy released due to bond forming. B-N dative bond is weak cmopared to C-C bond strength which is 376 kJ/mol.

Ng611 (talk) 23:29, 15 May 2018 (BST) Remember to cite your bond values (ideally from a textbook, databook, or paper)

BBr3

Optimization calculation summary

Item                     Value        Threshold    Converged?
Maximum Force            0.000025     0.000450     YES
RMS     Force            0.000015     0.000300     YES
Maximum Displacement     0.000125     0.001800     YES
RMS     Displacement     0.000078     0.001200     YES
Predicted change in Energy=-3.579173D-09

Frequency summary

Low frequencies ---   -4.9432    0.0001    0.0001    0.0001    2.2347    3.6178
Low frequencies ---  155.8962  155.9441  267.6992

The completed BH3 frequency *.log file is liked to here

Frequency analysis log file is linked here DOI:10042/202337

optimized BBr3 molecule


Al2Cl4Br2

five isomers and their symmetry


Monomer AlCl2Br

optimized Monomer AlCl2Br

The completed AlCl2Br frequency *.log file is liked to here

Frequency analysis log file is linked here DOI:10042/202353

Item                     Value        Threshold    Converged?
Maximum Force            0.000081     0.000450     YES
RMS     Force            0.000042     0.000300     YES
Maximum Displacement     0.001588     0.001800     YES
RMS     Displacement     0.000974     0.001200     YES
Predicted change in Energy=-1.810813D-07
Low frequencies ---    0.0023    0.0035    0.0043    1.3569    3.6367    4.2604
Low frequencies ---  120.5042  133.9178  185.8950

Isomer A with 2 bridging ions information

optimized Isomer A

The completed BH3 frequency *.log file is liked to here

Frequency analysis log file is linked here DOI:10042/202348

Item                     Value        Threshold    Converged?
Maximum Force            0.000067     0.000450     YES
RMS     Force            0.000023     0.000300     YES
Maximum Displacement     0.001141     0.001800     YES
RMS     Displacement     0.000499     0.001200     YES
Predicted change in Energy=-7.518420D-08
Low frequencies ---   -5.1730   -4.9021   -3.0082   -0.0013    0.0012    0.0013
Low frequencies ---   14.8117   63.2813   86.0726

Isomer B with trans terminal Br and bridging Cl

optimized Isomer B

The completed BH3 frequency *.log file is liked to here

Frequency analysis log file is linked here DOI:10042/202349

Item               Value     Threshold  Converged?
Maximum Force            0.000040     0.000450     YES
RMS     Force            0.000014     0.000300     YES
Maximum Displacement     0.001356     0.001800     YES
RMS     Displacement     0.000593     0.001200     YES
Predicted change in Energy=-1.805358D-08
Low frequencies ---   -0.0032   -0.0030   -0.0025    1.8920    1.9704    3.9624
Low frequencies ---   18.0988   49.0858   72.9223

Questions about isomers

1.determine the relative energy of these isomers in kJ/mol?

E(a)= -2352.40631 a.u.= -6175066 kJ/mol 
E(b)= -2352.41632 a.u.= -6175092 kJ/mol
E(a-b)= 26 kJ/mol
1 mole of Isomer A has 26 kJ more than 1 mole of isomer B.

2.discuss the relative stability of these conformers with respect to the bridging ions?

Isomer A is less stable than Isomer B because isomer B has bridging Br atoms which are lager with better orbital overlap.

3.determine the dissociation energy for the lowest energy conformer into 2AlCl2Br?

E(monomer)= -1176.19014 a.u.= -3087499 kJ/mol 
E(b)= -2352.41632 a.u.= -6175092 kJ/mol
E(dissociation)= -3087499*2-(-6175092)= 93 kJ/mol

4.is the product more or less stable than the isolated monomers?

The product dimer is more stable since heat will be released if bond is forming.


MOs of isomer B

Ng611 (talk) 23:36, 15 May 2018 (BST) You needed to look at 3 MOs as opposed to just one. You should also aim to format your MO analysis in the style that you learned in your MO course. The orbital that you've analysed is correct however, well done.


Ng611 (talk) 23:38, 15 May 2018 (BST) A good report overall. Excellent first section. You let yourself down with your MO analysis in the second section (you needed to analyse more than 1 MO) as well as with a few minor errors here and there, but otherwise good.