Photoluminescence

CHEM6813
Tristan Theunissen, 2015074863

Luminescence specifically refers to the spontaneous light emission by an atom

or molecule system that was generated without heating (or change of
temperature), and thus is referred to commonly as ‘cold light’.
Fluorescence occurs when an atom (and some molecules) becomes excited to
either the first, S1, or second, S2, higher energy singlet state, then rapidly (10-8s)
loses the energy as a photon (of the same energy that excited it) to enter its
ground state, S0. The decay of the luminescence is essentially independent of
temperature. Fluorescence emission in molecules proceeds by a photon being
emitted by the system at a lower energy, or longer wavelength than that of
excitation. This is a unique feature of molecular fluorescence as the light emitted
is ‘red-shifted’ or Stoke’s shifted (Stoke’s Law).
Phosphorescence operates in a similar manner to that of fluorescence, however,
differs in the length of the afterglow lifetime (10-4 – 10-2 s), as well as a change in
multiplicity. The change in the magnetic spin (multiplicity) of the excited electron
is done via a process known as intersystem crossing. The electron now exists in
a new excited state called a triplet state, (T1). Phosphorescence occurs as the
system relaxes back to its ground state (radiative decay).
Luminescence relaxation mechanism is depicted in Fig. 1 where there are two
types of decay to the ground state; one radiative and the other non-radiative. The
process of luminescence occurs via the former. The latter, non-radiative process,
occurs when the radiative energy is converted to vibrations that transport the
energy in the form of heat (thermal degradation) to the surroundings.

Figure 1. Luminescence relaxation mechanism using a Jablonski diagram. Radiative and non-radiative
transitions are depicted by straight and wavy arrows, respectively.
Depending on the duration of the emission, luminescence can be further sub-
categorized:
(a) Fluorescence – most atoms or molecules at room temperature occupy the
lowest vibronic level of the ground electronic state, and on absorption of
electromagnetic radiation are elevated to produce excited states. The simplified
Fig. 2 below depicts the absorption by molecules to the first, S1, excited state:

Figure 2. The straight up arrows indicate excitation with photons of higher energy. Emission of light in
molecules can lose energy through internal conversion between vibronic levels ν1, ν2, ν3, ν4 in S1 and then
as fluorescent light which is Stoke’s shifted.

(b) Phosphorescence – during the production of the excitation of an electron into

a higher orbital, the spin direction of the electron is preserved, still maintaining
the opposite spin pairing. The spin of the excited electron is then reversed by a
process known as intersystem crossing (singlet-to-triplet) as the electron enters
a lower energy ‘forbidden’ state known as a triplet state (T1). Radiative decay
back to the ground state S0 is slow, thus, may survive for microseconds or longer.
Fig. 3 below indicates the process of phosphorescence:

Figure 3. The straight up arrow indicates excitation light. Emission in some molecules show intersystem
crossing, indicated by the dashed arrow, that results in phosphorescence.
Luminescence spectra are plotted as a measure of intensity of the emitted
radiation as a function of either the excitation wavelength or the emission
wavelength:
An excitation (absorbance) spectrum is generated by observing emission at a
fixed wavelength while the excitation wavelength is varied. When corrections for
variations are accounted for; the excitation spectrum and absorbance spectrum
are nearly identical to one another.
In an emission (fluorescence) spectrum a fixed wavelength is used to excite
the analyte, while the intensity of the emitted radiation is observed as a function
of wavelength. A molecule only has one excitation spectrum, but two emission
spectra: one for fluorescence and the other for phosphorescence.
Singlet state refers to when an electron is excited it is promoted in the same spin
orientation as it was when in the ground state (paired). The singlet is derived
using the spin multiplicity equation: 2S+1, where S is the sum of all electron spins.
Spins are denoted as either spin up (s = +1/2) or spin down (s = -1/2). S calculated
for the excited singlet state would be 2(1/2-1/2) + 1 = 1.
Triplet state refers to when an electron is excited it is promoted in the same spin
orientation (parallel) as the other unpaired electron. The triplet is derived using
the spin multiplicity equation: 2S+1, where S is the sum of all electron spins. Spins
are denoted as either spin up (s = +1/2) or spin down (s = -1/2). S calculated for
the excited triplet state would be 2(1/2+1/2) + 1 = 3. Although the triplet excited
state is slightly lower in energy than that of the singlet excited state; the process
is often referred to as the ‘forbidden transition’ due to its low probability of
occurring as it seemingly violates the spin selection rule.
Intersystem crossing refers to one particular path that a molecule may take in
order to divest itself of the excess energy it absorbed and return to its ground
(resting) state. This process causes the spin multiplicity of the electrons to change
from an excited singlet state (S1) to an excited triplet state (T1). This process can
only occur when the lowest vibronic level of the singlet state has similar energy
to that of an upper vibronic level of the triplet state. Once this happens it is
generally difficult for the molecule to return to its ground state, as it must first deal
with an additional spin flip, then followed by a change in electronic energy level,
which may take the molecule as much as 10-4 – 10 s to accomplish.
Applications include:
1. Medical - Fluorescence is widely used in analytical work of various compounds
present in cells of liver, kidney, etc. The sensitivity and selectivity of PL in many
micro systems facilitates the professionals to estimate amino acids, proteins and
nucleic acid in medico-legal works. Many blood tests are using luminescence
technique to determine and quantify the bacteria, and viruses.
2. Chemical analysis - If the different elements in a sample emit their
characteristics lines by electron or X-ray bombardment, then these elements may
be identified by analysing the emitted radiation. Measurement of coating
thickness on one chemical to another can be made by studying intensity and
characteristic emission from the material; chemical behaviour of liquids can also
be studied by fluorescence emission method.
References
1. O’Hara, P. B., St. Peter, W., & Engelson, C. (2005). Turning on the Light:
Lessons from Luminescence. Journal of Chemical Education, 82(1), 49.
2. Valeur, B., & Berberan-Santos, M. N. (2011). A Brief History of Fluorescence
and Phosphorescence before the Emergence of Quantum Theory. Journal of
Chemical Education, 88(6), 731–738.
3. Murthy, K. V. R., & Virk, H. S. (2013). Luminescence Phenomena: An
Introduction. Defect and Diffusion Forum, 347, 1–34.
4. Lakowicz, Joseph R. (1999). Principles of Fluorescence Spectroscopy. Kluwer
Academic / Plenum Publishers. ISBN 978-0-387-31278-1.
5. Rye, H. S., Dabora, J. M., Quesada, M. A., Mathies, R. A., & Glazer, A. N.
(1993). Fluorometric Assay Using Dimeric Dyes for Double- and Single-Stranded
DNA and RNA with Picogram Sensitivity. Analytical Biochemistry, 208(1), 144–
150.