Fluorescence and phosphorescence

These phenomena are closely related to electronic absorption spectra and can be used as a tool for
analysis and structure determination. Both involve the absorption of radiation via an electronic transition,
a loss of energy through either vibrational energy decay or nonradiative processes, and the subsequent
emission of radiation of a lower frequency than that absorbed.

Electrons possess intrinsic magnetic moments that are related to their spin angular momenta. The spin
quantum number is s = 1/2, so in the presence of a magnetic field an electron can have one of two
orientations corresponding to magnetic spin quantum number ms = ±1/2. The Pauli exclusion
principle requires that no two electrons in an atom have the same identical set of quantum numbers;
hence when two electrons reside in a single AO or MO they must have different ms values (i.e., they are
antiparallel, or spin paired). This results in a cancellation of their magnetic moments, producing a so-
called singlet state. Nearly all molecules that contain an even number of electrons have singlet ground
states and have no net magnetic moment (such species are called diamagnetic). When an electron absorbs
energy and is excited to a higher energy level, there exists the possibility of (1) retaining its antiparallel
configuration relative to the other electron in the orbital from which it was promoted so that the molecule
retains its singlet characteristic, or (2) changing to a configuration in which its magnetic moment is
parallel to that of its original paired electron. In the latter case, the molecule will possess a net magnetic
moment (becoming paramagnetic) and is said to be in a triplet state. For each excited electronic state,
either electron spin configuration is possible so that there will be two sets of energy levels (see Figure 9).
The normal selection rules forbid transitions between singlet (Si) and triplet (Ti) states; hence there will be
two sets of electronic transitions, each associated with one of the two sets of energy levels.

Fluorescence

Fluorescence is the process whereby a molecule in the lower of two electronic states (generally the ground
state) is excited to a higher electronic state by radiation whose energy corresponds to an allowed
absorption transition, followed by the emission of radiation as the system decays back to the original
state. The decay process can follow several pathways. If the decay is back to the original lower state, the
process is called resonance fluorescence and occurs rapidly, in about one
nanosecond. Resonance fluorescence is generally observed for monatomic gases and for many organic
molecules, in particular aromatic systems that absorb in the visible and near-ultraviolet regions. For many
molecules, especially aromatic compounds whose electronic absorption spectra lie predominately in the
shorter-wavelength ultraviolet region (below 400 nanometres), the lifetime of the excited electronic state
is sufficiently long that prior to the emission of radiation the molecule can (1) undergo a series
of vibrational state decays, (2) lose energy through interstate transfer (intersystem crossing), or (3) lose
vibrational energy via molecular collisions.

In the first case, the system will emit radiation in the infrared region as the vibrational energy of the
excited state decays back to the lowest vibrational level. The molecule then undergoes an electronic state
decay back to one of the vibrational states associated with the lower electronic state. The resulting
emission spectrum will then be centred at a frequency lower than the absorption frequency and will
appear to be a near mirror image of the absorption spectrum. The second mechanism can be illustrated by
reference to the potential energy curves for nitrogen hydride (NH) shown in Figure 7B. The curves for
the 1Σ+ and 1Π states intersect at a radius value of 0.2 nanometre. If a molecule in the 1Π excited electronic
state is in a vibrational level corresponding to the energy value of this intersection point, it can cross over
to the 1Σ+ state without emission or absorption of radiation. Subsequently it can undergo vibrational
energy loss to end up in the lowest vibrational state of the 1Σ+ electronic state. This can then be followed by
an electronic transition back to the lower 1Δ state. Thus the absorption of energy corresponding to an
original 1Δ → 1Π transition results in the emission of fluorescence radiation corresponding to the lower
frequency 1Σ+ → 1Δ transition. In the third case, when two molecules collide there exists the possibility for
energy transfer between them. Upon colliding, a molecule can thus be transformed into a different
electronic state whose energy minimum may lie lower or higher than its previous electronic state.
The lifetimes of the excited singlet electronic states, although long enough to allow vibrational relaxation
or intersystem crossing, are quite short, so that fluorescence occurs on a time scale of milliseconds to
microseconds following irradiation of a material. The most common mode of observation of fluorescence
is that of using ultraviolet radiation (invisible to the human eye) as an exciting source and observing the
emission of visible radiation. In addition to its use as a tool for analysis and structural determination of
molecules, there are many applications outside the laboratory. For example, postage stamps may be
tagged with a visually transparent coating of a fluorescing agent to prevent counterfeiting, and the
addition of a fluorescing agent with emissions in the blue region of the spectrum to detergents will impart
to cloth a whiter appearance in the sunlight.

Phosphorescence

Phosphorescence is related to fluorescence in terms of its general mechanism but involves a slower decay.
It occurs when a molecule whose normal ground state is a singlet is excited to a higher singlet state, goes
to a vibrationally excited triplet state via either an intersystem crossing or a molecular collision, and
subsequently, following vibrational relaxation, decays back to the singlet ground state by means of a
forbidden transition. The result is the occurrence of a long lifetime for the excited triplet state; several
seconds up to several hours are not uncommon. These long lifetimes can be related to interactions
between the intrinsic (spin) magnetic moments of the electrons and magnetic moments resulting from the
orbital motion of the electrons.

Molecules in singlet and triplet states react chemically in different manners. It is possible to
affect chemical reactions by the transfer of electronic energy from one molecule to another in the reacting
system. Thus the study of fluorescence and phosphorescence provides information related to chemical
reactivity.