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Absorption Wavelength Prediction of

a Conjugated Dye Series Using a


Computational Method

JORDAN HASKINS
AMANDA PETTY
GINO MOORE
ANDREW FLEMING
Introduction

In this experiment, we used the HMO and Spartan


computer programs in order to calculate the
molecular orbital energies of the three conjugated
dyes used in Experiment 11.
The dyes used were:
 1,1' diethyl-4,4'-cyanine iodide
 1,1' diethyl-4,4'-carbocyanine

 1,1' diethyl-4,4'-dicarbocyanine iodide


Materials and Methods

Instructions were followed from the handout given


by the instructor for Spartan ’04 and instructions
from the Physical Chemistry Lab Manual for HMO
by Trinity Software.
Next the molecular orbital energies were calculated
for each dye using both programs.
Calculations were made to determine wavelength
and frequency.
These values and the FEMO values from
Experiment 11 were compared.
1,1’-diethyl-4,4’-cyanine iodide
1,1’-diethyl-4,4’-carbocyanine iodide
1,1’-diethyl-4,4’-dicarbocyanine iodide
Calculations

Equations:
ΔE= LUMO – HOMO
ΔE= hc/λ
ν= c/λ

Avalue of -75 kcal/mol was given in the lab


manual for β (used for calculation of
molecular orbital energy).
Results
Dye FEMO FEMO HMO HMO Spartan Spartan
LUMO, HOMO, LUMO, HOMO, LUMO, (J) HOMO, (J)
(J) (J) (J) (J)

1,1’-diethyl-
4,4’-cyanine 1.11 x 10-18 7.68 x 10-19 -6.89 x 10-20 5.66 x 10-20 -7.34 X 10-19 -1.70 X 10-18
iodide

1,1’-diethyl-
4,4’-carbocyani 1.05 x 10-18 7.68 x 10-19 -6.01 x 10-20 7.40 x 10-20 -7.95 X 10-19 -1.57 X 10-18
ne iodide

1,1’-diethyl-
4,4’-dicarbocya 1.00 x 10-18 7.68 x 10-19 -5.78 x 10-20 4.42 x 10-20 -8.01 X 10-19 -1.50 X 10-18
nine iodide
Results

Dyes ΔEFEMO (J) ΔEHMO (J) ΔESPTN (J)

1,1’-diethyl- 3.38 x 10-19 4.08 x 10-19 9.69 x 10-19


4,4’-cyanine
iodide
1,1’-diethyl- 2.77 x 10-19 4.36 x 10-19 7.77 x 10-19
4,4’-carbocyanine
iodide
1,1’-diethyl- 2.35 x 10-19 3.32 x 10-19 7.02 x 10-19
4,4’-dicarbocyanin
e iodide
Results
Dye FEMO, Percent HMO, Percent Spartan, Percent
λmax (m) Error λmax (m) Error λmax (m) Error

1,1’-diethyl-
4,4’-cyanine 5.90 x 10-7 0.36 4.87 x 10-7 17.2 2.05 x 10-7 65.2
iodide

1,1’-diethyl-
4,4’-carbocyani 7.08 x 10-7 1.16 4.55 x 10-7 36.4 2.56 x 10-7 63.9
ne iodide

1,1’-diethyl-
4,4’-dicarbocya 8.14 x 10-7 3.67 5.98 x 10-7 29.2 2.83 x 10-7 65.2
nine iodide
Results
Dye FEMO, FEMO, ν at HMO, λmax HMO, ν at Spartan, Spartan, ν at
λmax (m) λmax (s-1) (m) λmax (s-1) λmax (m) λmax (s-1)

1,1’-diethyl-
4,4’-cyanine 5.90 x 10-7 5.08 x 1014 4.87 x 10-7 6.16 x 1014 2.05 x 10-7 1.46 x 1015
iodide

1,1’-diethyl-
4,4’-carbocyanin 7.08 x 10-7 4.24 x 1014 4.55 x 10-7 6.58 x 1014 2.56 x 10-7 1.17 x 1015
e iodide

1,1’-diethyl-
4,4’-dicarbocyan 8.14 x 10-7 3.69 x 1014 5.98 x 10-7 5.01 x 1014 2.83 x 10-7 1.06 x 1015
ine iodide
Discussion

The FEMO and HMO calculations obtained from


these experiments were very similar in
HOMO,LUMO, wavelength and frequency.

However, the values obtained from Spartan were not


similar. This could be due to Spartan’s inability to
build these dyes perfectly planar.
Conclusions

•The percent error for our Spartan value was higher


than our percent errors for FEMO and HMO. This is
due to the fact that Spartan could not produce planar
molecules of the dyes. Therefore, the data produced by
Spartan were not as accurate as those from HMO.
•Thus, we concluded that the HMO software is more
suitable for calculations such as these.
Citations

Clark, Roy W.; Howard, James C. Physical Chemistry Lab


Manual, 4th ed., RonJon Publishing, Denton, TX, 1996.
Fleming, A.J.; Physical Chemistry Laboratory Notebook,
2007 p. 12-14.
Haskins, J.R.; Physical Chemistry Laboratory Notebook,
2007 p. 19-20.
Moore, L.G.; Physical Chemistry Laboratory Notebook, 2007
p. 14-15.
Petty, A..; Physical Chemistry Laboratory Notebook, 2007 p.
12-14.
Howard, James C. Spartan ’04 for Windows
Instructions.