CHEM 332L Physical Chemistry Laboratory Revision 1.

Electronic Spectra of Cyanine Dyes: A Particle in the Box Model

In this laboratory exercise we will examine the Visible Spectra of a series of Cyanine Dye molecules and determine max for each compound. These results will then be compared with max values obtained by treating the conjugated electrons of the molecules as a free-electron gas confined to a one-dimensional box whose length is that of the molecule. Consider the dye 1,1'-diethyl-4,4'-cyanine iodide:

The conjugated series of double bonds 1-4 extends from the Nitrogen atom on one end of the molecule to the Nitrogen atom on the opposite end. The N electrons (10 e- 's in this case): N = 2j + 2 where j = # of double bonds
(Eq. 1)

involved in this conjugated system can be thought of as occupying molecular electronic states according to the Pauli Exclusion Principle.

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An electronic transition can occur from the Highest Occupied Molecular Orbital (HOMO) to the Lowest Unoccupied Molecular Orbital (LUMO) when a photon with an appropriate energy Ephoton is absorbed by the molecule. Ephoton = E = Thus, E for the transition can be determined by measuring the max for the dye. To a first approximation, these N electrons in the conjugated system of the molecule can be modeled as a free electron gas confined to a one-dimensional box of length equal to that of the conjugated chain, designated L for our purposes. Based on the length of the C=C bonds involved in the conjugated chain, L can be determined according to: L = Nxl where l = length of C=C bond = 139 pm
(Eq. 4) (Eq. 2) (Eq. 3)

(According to Kuhn, the length of the conjugated chain should be taken as "the length of the polymethine ziz-zag chain between the nitrogen atoms plus one bond distance to either side.") Using this model, the molecule's electronic energy levels can be approximated using the solutions to the "Particle in a Box's" Schrodinger Wave Equation: En = n = 1, 2, 3,
(Eq. 5)

The HOMO-LUMO transition will then occur between the N/2 and the N/2+1 levels. Thus, we can estimate E according to: E = EN/2+1 - EN/2 = 1 = 1
(Eq. 6) (Eq. 7)

This result can then be used to predict the max for the compound's spectrum. This prediction can then be compared directly with the measured result. Based on the Particle in a Box model, we expect the electronic transition to produce a fairly sharp spectral band. However, for solutions of these compounds, the spectral band is observed to be fairly broad; on the order of tens of nanometers.

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If the electron transitions within a time interval much shorter than that of a molecular vibration, the absorption from many molecules shows up as a broad band; those molecules that have their conjugated bond system stretched or compressed during a transition, absorb at longer and shorter wavelengths than the absorption maximum, max. So, in this study, we will measure the max for a series of cyanine dyes and compare the results with those expected based on the Particle in a Box model. These results will then provide us with some insight into the electronic structure of these compounds.

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Procedure
Prepare 10-4 M Methanol solutions of the following three cyanine dyes:

Take the Visible Spectrum of each solution and determine max (include an error estimate) for each compound.

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Data Analysis
1. Determine max for each compound whose spectrum was taken, using the Particle in a Box model. Compare each result with the experimental value. Comment. Compare your experimentally determined max values with those of the literature. Comment.

2.

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References
Gerkin, Roger E. "A Molecular Spectral Corroboration of Elementary Operator Quantum Mechanics" J. Chem. Ed. 42 (1965) 490. Kuhn, Hans "A Quantum-Mechanical Theory of Light Absorption of Organic Dyes and Similar Compounds" J. Chem. Physics 17 (1949) 1198. Sime, Rodney J. Physical Chemistry: Methods, Techniques, and Experiments Saunders College Publishing, Philadelphia, 1990. Shoemaker, David P.; Garland, Carl W. and Nibler, Joseph W. Experiments in Physical Chemistry McGraw-Hill, New York, 1996.