Experiment

Absorption Band Spectrum and

Fluorescence Spectrum of Anthracene
Although the spectra of Anthracene will be too complex to permit a
detailed treatment, you should nevertheless consult the textbook for a
general discussion of the theory involved. In this experiment, the
absorption band spectrum and fluorescence spectrum of anthracene are to
be determined and compared, and certain features of the spectra should be
noted.

THEORY
Most organic molecules have an even number of electrons with all
electron spins paired in the ground state, which is usually referred to as So .
Promotion of an electron to a higher unoccupied orbital can result in either
a singlet or a triplet state. These latter singlet and triplet electronically
excited states are usually denoted in ascending energy order by S1 , S2 , . . ..
and T1 , T2 , . . .. , respectively , as shown in Fig. 1.
In a polyatomic molecule with n atoms the potential energy function
plotted versus interatomic distance generates a hypersurface with 3n-6
dimensions.

A hypersurface of 66 dimensions would be necessary to

represent completely the vibrational motions of the nuclei in an anthracene

molecule.

We simplify this by considering only the function along a

single "critical coordinate" as given in Fig. 1.

Although absorption A

B raises the molecule to a vibrationally

as well as an electronically excited state, the emission of resonance

fluorescence B

A , often observed in diatomic gases at low pressure,

is rare ( see following discussion). Often the absorption bands are weak
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( particularly in the S0

S1 transition ) , so that pressures of 50 mm or

more are necessary to observe fluorescence.

In gases at such pressures the

excited molecule collides many times with other molecules during its
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lifetime (~10 sec), and hence the molecule vibrationally equilibrates

quickly, dropping usually to the zeroth vibrational level before its radiates.
The detailed mechanism of this intermolecular vibrational energy transfer
(called relaxation) is not clearly understood, but it apparently proceeds
through a series of collisions rather than one total interchange of energy.

Fig-1Potential energy diagram, giving the shape of the hypersurface along a critical
coordinate for the ground state S0 and the first excited singlet S1 and triplet T1
states of a representative organic molecule in solution. G is a point of intersystem
crossing, S1 T1. Forconvenience in representation the distances r were chosen rso
rs1rr1 so the spectra are spread out. Actually, in complex, fairly symmetrical
molecules rso rs1rr1 and the 0-0 absorption and fluorescence bands almost
coincide, but phosphorescence bands are significantly displaced to the longer
wavelengths.

In a liquid, contact with other molecules is maintained at all times, so

that a molecule
such as anthracene with a singlet-singlet
radiatived lifetime
-8
4
of about 10 sec may be perturbed about 10 times before it emits
fluorescence. Thus, in solution, just as the gas at high pressure, resonance
fluorescence never appears, only transitions originating from the lowest
D in Fig. 1 ). The relative
vibrational levels, usually v' = 0 level (C
intensities of the resulting fluorescence bands, corresponding to the
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transitions ( v' = 0 )
( V"=V", . . ., 2, 1, 0 ) , depend partially on the
shapes and location of the potential curves along the critical coordinated.
Similarly, in absorption at room temperature transitions are usually
originated from the lowest v"=0 vibrational level of the ground state.
The distance between peaks in a fluorescence spectrum is a direct
measure of the energy differences between the vibrational levels of the
ground state of the fluorescing molecule. Conversely, the absorption
spectrum gives the spacing of the vibrational levels in the excited state of
the molecule.

-2

EXPERIMENT
(Sample cell)
1.,

2.

3.(Fluorescence Spectrophotometer)
(3-3)
4.

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CALCULATIONS
1. Convert all the absorption, excitation ( the one with emission
monochromator fixed at 400 nm ) , and fluorescence ( the one with
excitation monochromator fixed at 355 nm ) spectra to be plotted in
different colors as absorption versus wavenumber and relative emission
intensity versus wavenumber in a schematic diagram to show the
"similarity in appearance" of the absorption and excitation spectra and
to show the "mirror-image symmetry" between the absorption (or
excitation) and fluorescence spectra.
2. Assign the (0, 4') , (0, 3') , (0, 2') , (0, 1') , and (0, 0') bands in your
absorption spectrum (or excitation spectrum) and the (0', 0) , (0', 1) , (0',
2) , (0', 3) , and (0', 4) band in your fluorescence spectrum and depict
their corresponding transitions in a scheme of vibrational energy levels
associated with S0 and S1 and calculate the energies of the five
vibrational energy levels observed
both in the absorption and
-1
fluorescence spectra in Kcal . mole .
3. Express the vibrational spacing, in wave number of (0, 1) , (1, 2) , (2,
3) , and (3, 4) associated with S0 and those of (0', 1') , (1', 2') , (2', 3') ,
and (3', 4') associated with S1 in the above scheme.

DISCUSSION
1.All the fluorescence spectra obtained have the similar appearance, except
the emission intensity, independent of the excitation wavelength set at 340
or 355 or 375 nm. Gave your explanation.
S0) is not frequently observed under ordinary
2.Phosphorescence (T1
circumstances , neither in this experiment. Suggest an explanation.
3.Explain the nearly "mirror-image symmetry" observed in your spectra.

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