Molecular Orbital calculations of m-dichlorobenzene
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AM1 geometry optimization bond lengths
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AM1 geometry optimization gave a bond length value of 1.7 angstroms
between C-Cl bonds, 1.1 angstroms between C-H bonds,
and 1.4 angstroms or 1.39 angstroms between carbon bonds. The bond
length between carbon bonds varies slightly due to the high
electronegativity of chlorine present. The literature bond length value
for C-Cl bond is 1.77 angstroms, for C=C bond is 1.34 angstroms, for C-C
bond is 1.54 angstroms, and for H-C bond is 1.08 angstroms.7
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PM3 geometry optimization bond lengths
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PM3 geometry optimization gave a bond length value of 1.7 angstroms between C-Cl bonds, 1.1 angstroms between C-H bonds,
and 1.4 angstroms or 1.39 angstroms between carbon bonds. The bond
length between carbon bonds varies slightly due to the high
electronegativity of chlorine present.
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6-21G geometry optimization bond lengths
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6-21G geometry optimization gave a bond length value of 1.81 angstroms
between C-Cl bonds, 1.07 angstroms between C-H bonds, and 1.38 angstroms
between carbon bonds.
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6-31G geometry optimization bond lengths
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6-31G geometry optimization gave a bond length value of 1.81 angstroms between
C-Cl bonds, 1.07 angstroms between C-H bonds, and 1.38 angstroms or 1.39 angstroms
between carbon bonds. The bond
length between carbon bonds varies slightly due to the high
electronegativity of chlorine present.
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DZV geometry optimization bond lengths
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DZV geometry optimization gave a bond length value of 1.8 angstroms
between C-Cl bonds, 1.07 angstroms between C-H bonds, and 1.39 angstroms
between carbon bonds. This geometry matches the literature values
for the various bonds the closest, and is therefore the most accurate
calculation. This matched expectations that the largest basis set
(DZV) would produce the best results for the more complicated molecules.
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Highest occupied molecular orbital of m-dichlorobenzene
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This is the highest occupied molecular orbital (HOMO) at orbital 37.
Orbital 37 was chosen for the HOMO because m-dichlorobenzene has a total
number of 74 electrons, and the number of total electrons was divided
by two.
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Lowest unoccupied molecular orbital of m-dichlorobenzene
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This is the lowest unoccupied molecular orbital (LUMO) at orbital 38.
Orbital 38 was chosen as the LUMO because the HOMO is in orbital 37.
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The electrostatic potential of m-dichlorobenzene
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This is the electrostatic potential of m-dichlorobenzene. The red area
represents the lowest electrostatic potential and the blue area
represents the highest electrostatic potential. Intermediate colors
represent intermediate potentials.
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Partial atomic charges on each atom in m-dichlorobenzene
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The partial atomic charge on each atom is shown in the diagram on the
left. The values of the partial charges on each atom were created by
symmetrical distribution of electrons in the chemical bonds.
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Vibrational hydrogen stretch of m-dichlorobenzene
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The vibrational modes for m-dichlorobenzene were extracted from a file
built with the DZV basis set due to the DZV producing the best optimized
geometry for the molecule.
The hydrogen stretch that occurs at 3450.03 cm¯¹ of the m-dichlorobenzene molecule can be visualized in the diagram on the right.
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Vibrational hydrogen wiggle of m-dichlorobenzene
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The vibrational hydrogen wiggle that occurs at 1194.73 cm¯¹ of the
m-dichlorobenzene molecule can be visualized in the diagram on the left.
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Vibrational carbon wobble of m-dichlorobenzene
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The vibrational carbon wobble that occurs at 1171.71 cm¯¹ of the m-dichlorobenzene molecule can be visualized in the diagram on the right.
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Vibrational hydrogen jiggle of m-dichlorobenzene
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The vibrational hydrogen jiggle that occurs at 1624.18 cm¯¹ of the m-dichlorobenzene molecule can be visualized in the diagram on the left.
A reference IR spectrum for m-dichlorobenzene can be found at NIST.
The reference spectrum contains peaks that can be correlated to
the above four vibrational modes, these peaks and a comparison are
summarized below in Table 1. The calculated peaks all come within
reasonable distances of the reference peaks, which suggests that the
vibrational frequency calculations have some level of validity, though
are still questionable due to discrepancies in the dipole calculations
and UV-visible absorbance calculations produced by the DZV basis set.
Summary of calculated vibrational frequencies for m-dichlorobenzene
compared to values read from reference spectrum.
Reference Peaks
(values were estimated from spectrum)
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Calculated Peaks
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| 1125 cm¯¹ |
1171.71 cm¯¹ |
| 1200 cm¯¹ |
1194.73 cm¯¹ |
| 1580 cm¯¹ |
1624.18 cm¯¹ |
| 3125 cm¯¹ |
3450.03 cm¯¹ |
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The experimental dipole
moment for m-dichlorobenzene was calculated once with each basis set without the inclusion of any
diffuse functions. The dipole moment closest to the literature
value of 1.73 D
7 was 1.233658 D which was produced by the calculations run in the AM1
basis set. There was an error of 28.7% in the
best experimental dipole moment value compared to literature, which
suggests that the validity of the calculation is poor. The calculated
dipole moments from each basis set are summarized below in Table 2.
Table 2: Summary of the dipole moments calculated with each of the
5 basis sets. AM1 produced the closest to the literature value.
AM1
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1.233658 D
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PM3
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0.879663 D
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6-21G
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2.586725 D
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6-31G
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2.566443 D
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DZV
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2.499071 D
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The UV-visible absorption for m-dichlorobenzene was calculated using each of the three ab initio basis sets and compared to the literature range of 166.7-229.4 nm8 below. The calculated values that can be seen in Table 3 are reasonably far
below the minimum of the literature range. This discrepancy suggests
that the quantum calculations for m-dichlorobenzene are of questionable
validity.
Table 3: Summary of the frequencies of UV visible absorption
calculated from significant oscillator strengths
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Oscillator Strength
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Wavelength |
6-21G
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1.405637
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144.23 nm
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0.916539
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142.10 nm
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6-31G
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1.505648
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146.93 nm
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1.22601
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144.78 nm
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DZV
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1.489986
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150.09 nm
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1.156321
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148.59 nm
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Based on template by A. Herráez as modified by J. Gutow
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