Bromine

Bromine is a diatomic molecule with an atomic number of 35 on the periodic table. This section depicts the geometric optimization of Bromine (Br2)
Table 1: Computer method used with the resulting atomic orbitals and molecular orbitals generated by that method. Additionally the bond length generated by the subsequent methods.
Method
Atomic Orbitals used
Molecular Orbitals Generated
Bond Length (pm)
PM3
7
8
229
3-21G
35
46
244
6-31G
35
58
241
DZV
35
48
243
 

Figure 1: Graph of bond length vs energy for the ab inito basis sets. Zoomed in image is of the best geometry set from 6-21G.


Figure 2: Molecular orbital diagram for bromine (Br2) with respective molecular orbital cartoons. The anti bonding pi orbital is the highest occupied molecular orbital and the anti bonding sigma orbital is the lowest unoccupied molecular orbital. A better depiction of the HOMO and LUMO molecular orbitals for Br2 can be observed below. If the molecular orbital is lower in energy than the atomic orbital it is a bonding orbital and if the molecular orbital energy is higher than the atomic orbital it is an anti bonding orbital. 
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Bond Length of Bromine from PM3 geometry optimization.
The geometry optimizations for PM3, 3-21G, 6-21G, and DZV are shown below. Bond angles are not shown due to the molecule being 180 degrees.

Image to the right depicts the geometry optimization for PM3 with bond length. PM3 provided the closest bond length to the theoretical. This was due to bromine being used for the optimization parameters. That caused the calculated bond length to have a less than 1% error with the theoretical value of 0.228 nm2.
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Bond length of bromine with 3-21G geometry optimization.

Geometry optimization from ab inito theory 3-21G. 3-21G had to be done instead of 6-31G because it was not optimized for bromine.
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Bond Length of Bromine from DZV geometry optimization.

Geometry optimization from ab inito theory from DZV geometry optimization.
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Bond Length of Bromine from 6-31G geometry optimization.

Geometry optimization from ab inito theory from 6-31G geometry optimization.This proved to be the best when compared to the theoretical bond length.
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Geometry optimized bromine showing HOMO p orbitals in best geometry optimized basis set 6-31G.

Molecular orbital 35: p orbitals for the HOMO molecular orbitals.
HOMO=Highest Occupied Molecular Orbital
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Geometry optimized bromine showing LUMO p orbitals in best geometry optimized basis set 6-31G.

Molecular orbital 35: p orbitals for the LUMO molecular orbitals.
LUMO=Lowest Unoccupied Molecular Orbital
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