TOPIC 11G  Decay of excited states

➤  Why do you need to know this material?

Phosphorescence

Emission intensity, I
Much information about the electronic structure of a mol-
ecule can be obtained by observing the radiative decay of
excited electronic states back to the ground state. Such
decay is also used in lasers, which are of exceptional tech-
nological importance.
Fluorescence

➤  What is the key idea?

Molecules in excited electronic states discard their excess
energy by emission of electromagnetic radiation, transfer
as heat to the surroundings, or fragmentation.
➤  What do you need to know already?
You need to be familiar with electronic transitions in mole-
cules (Topic 11F), the difference between spontaneous and
stimulated emission of radiation (Topic 11A), and the gen-
eral features of spectroscopy (Topic 11A). You need to be
aware of the difference between singlet and triplet states
(Topic 8C) and of the Franck–Condon principle (Topic 11F).
Radiative decay is a process in which a molecule discards
its excitation energy as a photon (Topic 11A); depending
on the nature of the excited state, this process is classified as
either fluorescence or phosphorescence. A more common fate
of an electronically excited molecule is non-radiative decay,
in which the excess energy is transferred into the vibration,
rotation, and translation of the surrounding molecules. This
thermal degradation converts the excitation energy into ther-
Time, t
Figure 11G.1  The empirical (observation-based) distinction
between fluorescence and phosphorescence is that the former is
extinguished very quickly after the exciting radiation is removed,
whereas the latter continues with relatively slowly diminishing
intensity.
of seconds). The difference suggests that fluorescence is a fast
conversion of absorbed radiation into re-emitted energy, and
that phosphorescence involves the storage of energy in a
reservoir from which it slowly leaks.
Figure 11G.2 shows the sequence of steps involved in fluo-
rescence from molecules in solution. The initial stimulated
absorption takes the molecule to an excited electronic state; if
the absorption spectrum were monitored it would look like the
Radiationless
Molecular potential energy, V

decay
mal motion of the environment (i.e. to ‘heat’). An excited mol-
ecule may also dissociate or take part in a chemical reaction
(Topic 17G). Stimulated emission from excited states is the
Emission
key process that can lead to laser action. (fluorescence)
Absorption

11G.1  Fluorescence and

phosphorescence
In fluorescence, spontaneous emission of radiation occurs
while the sample is being irradiated and ceases as soon as
the exciting radiation is extinguished (Fig. 11G.1). In phos-
phorescence, the spontaneous emission may persist for long
periods (even hours, but more commonly seconds or fractions
Internuclear separation, R
Figure 11G.2  The sequence of steps leading to fluorescence
by molecules in solution. After the initial absorption, the upper
vibrational states undergo radiationless decay by giving up energy
to the surrounding molecules. A radiative transition then occurs
from the vibrational ground state of the upper electronic state.

Intensity, I
(0,0)
Absorption Fluorescence
Wavelength, λ
Figure 11G.3  An absorption spectrum (blue) shows vibrational
structure characteristic of the upper electronic state. A
fluorescence spectrum (purple) shows structure characteristic
of the lower state; it is also displaced to lower frequencies (but
the 0–0 transitions are coincident) and is often a mirror image
of the absorption spectrum.
one shown in Fig. 11G.3a. The excited molecule is subjected to
collisions with the surrounding molecules, and as it gives up
energy to them non-radiatively it steps down (typically within
picoseconds) the ladder of vibrational levels to the lowest vi-
brational level of the excited electronic state. The surround-
ing molecules, however, might now be unable to accept the
larger energy difference needed to lower the molecule to the
ground electronic state. The excited electronic state might
therefore survive long enough to undergo spontaneous emis-
sion and emit the remaining excess energy as radiation. The
downward electronic transition is vertical, in accord with the
Franck–Condon principle (Topic 11F), and the fluorescence
spectrum has vibrational structure characteristic of the lower
electronic state (Fig. 11G.3b).
Provided they can be seen, the 0–0 absorption and fluo-
rescence transitions (where the numbers are the values of vf
and vi, the vibrational quantum numbers for the final and
initial states) can be expected to be coincident. The absorp-
tion spectrum arises from 0 ← 0, 1 ← 0, 2 ← 0, … transitions
which occur at progressively higher wavenumbers (shorter
wavelengths) and with intensities governed by the Franck–
Condon principle. The fluorescence spectrum arises from
0 → 0, 0 → 1, … downward transitions which occur with
decreasing wavenumbers (longer wavelengths). The 0–0 ab-
sorption and fluorescence peaks are not always exactly coin-
cident, however, because the solvent may interact differently
with the solute in the ground and excited electronic states
(for instance, the hydrogen bonding pattern might differ).
Because the solvent molecules do not have time to rearrange
during the transition, the absorption occurs in an environ-
ment characteristic of the solvated ground state; however, the
fluorescence occurs in an environment characteristic of the
solvated excited state (Fig. 11G.4).
11G  Decay of excited states  471
Relaxation
Absorption Fluorescence
Figure 11G.4  The solvent can shift the fluorescence spectrum
relative to the absorption spectrum. On the left absorption occurs
with the solvent (depicted by the ellipses) in the arrangement
characteristic of the ground electronic state of the molecule (the
central blob). However, before fluorescence occurs, the solvent
molecules relax into a new arrangement, and that arrangement
is preserved during the subsequent radiative transition, the
fluorescence.
Fluorescence occurs at lower frequencies than the incident
radiation because the emissive transition occurs after some
vibrational energy has been discarded into the surroundings.
The vivid oranges and greens of fluorescent dyes are an every-
day manifestation of this effect: they absorb in the ultravio-
let and blue, and fluoresce in the visible. The mechanism also
suggests that the intensity of the fluorescence ought to depend
on the ability of the solvent molecules to accept the electronic
and vibrational quanta. It is indeed found that a solvent com-
posed of molecules with widely spaced vibrational levels (such
as water) can in some cases accept the large quantum of elec-
tronic energy and so extinguish, or ‘quench’, the fluorescence.
The rate at which fluorescence is quenched by other molecules
also gives valuable kinetic information (Topic 17G).
Figure 11G.5 shows the sequence of events leading to phos-
phorescence for a molecule with a singlet ground state (de-
noted S0). The first steps are the same as in fluorescence, but
the presence of a triplet excited state (T1) at an energy close to
that of the singlet excited state (S1) plays a decisive role. The
singlet and triplet excited states share a common geometry at
the point where their potential energy curves intersect. Hence,
if there is a mechanism for unpairing two electron spins (and
achieving the conversion of ↑↓ to ↑↑), the molecule may
undergo intersystem crossing, a non-radiative transition
between states of different multiplicity, and become a tri-
plet state. As in the discussion of atomic spectra (Topic 8C),
singlet–triplet transitions may occur in the presence of spin–
orbit coupling. Intersystem crossing is expected to be impor-
tant when a molecule contains a moderately heavy atom (such
as sulfur), because then the spin–orbit coupling is large.
Once an excited molecule has crossed into a triplet state, it
continues to discard energy into the surroundings. However, it
is now stepping down the triplet’s vibrational ladder and ends
472  11  Molecular spectroscopy

S1 T1 S0
35 IC
Molecular potential energy, V

S1

ν/(103 cm–1)
30 ISC
T1 25
Phosphorescence

Wavenumber, ∼
20
Fl Ph 471
ISC uo os n
Absorption S0 15 31 re ph m
5 sc or
nm e es
10 nc ce
e nc
6 e

Internuclear separation, R
Figure 11G.5  The sequence of steps leading to phosphorescence.
The important step is the intersystem crossing (ISC), the switch
from a singlet state (S1) to a triplet state (T1) brought about by
spin–orbit coupling. The triplet state acts as a slowly radiating
reservoir because the return to the ground state is spin-forbidden.
in its lowest vibrational level. The triplet state is lower in en-
ergy than the corresponding singlet state (Hund’s rule, Topic
8B). The solvent cannot absorb the final, large quantum of
electronic excitation energy, and the molecule cannot radiate
its energy because return to the ground state is spin-forbidden.
The radiative transition, however, is not totally forbidden
because the spin–orbit coupling that was responsible for the
intersystem crossing also weakens the selection rule. The mol-
ecules are therefore able to emit weakly, and the emission may
continue long after the original excited state was formed.
This mechanism accounts for the observation that the
excitation energy seems to get trapped in a slowly leaking
reservoir. It also suggests (as is confirmed experimentally) that
phosphorescence should be most intense from solid samples:
energy transfer is then less efficient and intersystem crossing
has time to occur as the singlet excited state steps slowly past
the intersection point. The mechanism also suggests that the
phosphorescence efficiency should depend on the presence of
a moderately heavy atom (with strong spin–orbit coupling),
which is in fact the case.
The various types of non-radiative and radiative transitions
0
Figure 11G.6  A Jablonski diagram (here, for naphthalene) is a
simplified portrayal of the relative positions of the electronic
energy levels of a molecule. Vibrational levels of states of a
given electronic state lie above each other, but the relative
horizontal locations of the columns bear no relation to the
nuclear separations in the states. The ground vibrational states
of each electronic state are correctly located vertically but the
other vibrational states are shown only schematically. (IC: internal
conversion; ISC: intersystem crossing.)
11G.2  Dissociation and predissociation
A chemically important fate for an electronically excited
molecule is dissociation, the breaking of bonds (Fig. 11G.7).
The onset of dissociation can be detected in an absorption
spectrum by noting that the vibrational fine structure of a
band terminates at a certain frequency. Absorption occurs
in a continuous band above this dissociation limit because
the final state is an unquantized translational motion of the
fragments. Locating the dissociation limit is a valuable way of
determining the bond dissociation energy.
In some cases, the vibrational structure disappears but
resumes at higher frequencies of the incident radiation. This
Continuum
Molecular potential energy, V

that can occur in molecules are often represented on a sche- Dissociation limit
matic Jablonski diagram of the type shown in Fig. 11G.6.

Brief illustration 11G.1

Fluorescence efficiency decreases, and the phosphorescence

efficiency increases, in the series of compounds: naphthalene,
1-chloronaphthalene, 1-bromonaphthalene, 1-iodonaphthalene.
The replacement of an H atom by successively heavier atoms
Internuclear separation, R
enhances intersystem crossing from S1 into T1, thereby decreas-
ing the efficiency of fluorescence. The rate of the radiative tran- Figure 11G.7  When absorption occurs to unbound states of
sition from T1 to S0 is also enhanced by the presence of heavier the upper electronic state, the molecule dissociates and the
atoms, thereby increasing the efficiency of phosphorescence. absorption spectrum is a continuum. Below the dissociation limit
the electronic spectrum shows a normal vibrational structure.
 11G  Decay of excited states  473

Continuum
11G.3  Lasers
Molecular potential energy, V
Dissociation limit

An excited state can be driven to discard its excess energy by

Continuum using radiation to induce stimulated emission. The word laser
is an acronym formed from light amplification by stimulated
emission of radiation. In stimulated emission (Topic 11A), an
excited state is stimulated to emit a photon by radiation of the
same frequency: the more photons that are present, the greater
is the probability of emission.
Internuclear separation, R Laser radiation has a number of striking characteristics
(Table 11G.1). Each of them (sometimes in combination
Figure 11G.8  When a dissociative state crosses a bound state, as in
with the others) opens up interesting opportunities in phys-
the upper part of the illustration, molecules excited to levels near
the crossing may dissociate. This predissociation is detected in the
ical chemistry. Raman spectroscopy (Topics 11B–D) has
spectrum as a loss of vibrational structure that resumes at higher flourished on account of the high intensity of monochro-
frequencies. matic radiation available from lasers, and the ultrashort
pulses that lasers can generate make possible the study of
light-initiated reactions on timescales of femtoseconds and
effect provides evidence of predissociation, which can be in- even attoseconds.
terpreted in terms of the molecular potential energy curves One requirement of laser action is the existence of a meta-
shown in Fig. 11G.8. When a molecule is excited to a high vi- stable excited state, an excited state with a long enough life-
brational level of the upper electronic state, its electrons may time for it to undergo stimulated emission. For stimulated
undergo a redistribution that results in it undergoing an in- emission to dominate absorption, it is necessary for there to
ternal conversion, a radiationless conversion to another elec- be a population inversion in which the population of the ex-
tronic state of the same multiplicity. An internal conversion cited state is greater than that of the lower state. Figure 11G.9
occurs most readily at the point of intersection of the two illustrates one way to achieve population inversion indirectly
molecular potential energy curves, because there the nuclear through an intermediate state I. Thus, the molecule or atom
geometries of the two electronic states are the same. The state is excited to I, which then gives up some of its energy non-
into which the molecule converts may be dissociative, so radiatively (for example, by passing energy on to vibrations of
the states near the intersection have a finite lifetime and hence the surroundings) and changes into a lower state B. The laser
their energies are imprecisely defined (as a result of lifetime
broadening, Topic 11A). As a result, the absorption spectrum
is blurred. When the incoming photon brings enough energy Table 11G.1  Characteristics of laser radiation and their chemical
to excite the molecule to a vibrational level high above the in- applications
tersection, the internal conversion does not occur (the nuclei
are unlikely to have the same geometry). Consequently, the Characteristic Advantage Application
levels resume their well-defined, vibrational character with High power Multiphoton process Spectroscopy
correspondingly well-defined energies, and the line structure Low detector noise Improved sensitivity
resumes on the high-frequency side of the blurred region. High scattering Raman spectroscopy
 intensity   (Topics 11B–11D)
Brief illustration 11G.2 Monochromatic High resolution Spectroscopy
State selection Photochemical studies
The O2 molecule absorbs ultraviolet radiation in a transition   (Topic 17G)
from its 3Σg− ground electronic state to a 3Σu− excited state that is Reaction dynamics
energetically close to a dissociative 3Πu state. In this case, the   (Topic 18D)
effect of predissociation is more subtle than the abrupt loss Collimated beam Long path lengths Improved sensitivity
of vibrational–rotational structure in the spectrum; instead, Forward-scattering Raman spectroscopy
the vibrational structure simply broadens rather than being  observable   (Topics 11B–11D)
lost completely. As before, the broadening is explained by the Pulsed Precise timing of Fast reactions
short lifetimes of the excited vibrational states near the inter-  excitation   (Topics 17G, 18C)
section of the curves describing the bound and dissociative Relaxation (Topic 17C)
excited electronic states. Energy transfer (Topic 17G)
474  11  Molecular spectroscopy
Radiationless
I transition
B The neodymium laser is an example of a four-level solid-
Energy
Pump Laser
transition
A A neodymium laser operates at a number of wavelengths in
X
Relaxation
Figure 11G.9  The transitions involved in a four-level laser. Because
the laser transition terminates in an excited state (A), the population
inversion between A and B is much easier to achieve than when the
lower state of the laser transition is the ground state, X.
transition is the return of B to a lower state A. Because four lev-
els are involved overall, this arrangement leads to a four-level
laser. One advantage of this arrangement is that the population
inversion of the A and B levels is easier to achieve than one in-
volving the heavily populated ground state. The transition from
X to I is caused by irradiation with intense light (either con-
tinuously or as a flash) in the process called pumping. In some
cases pumping is achieved with an electric discharge through
xenon or with the radiation from another laser.
Checklist of concepts
☐ 1. Fluorescence is radiative decay between states of the
same multiplicity; it ceases soon after the exciting
radiation is removed.
☐ 2. Phosphorescence is radiative decay between states
of different multiplicity; it persists after the exciting
radiation is removed.
☐ 3. Intersystem crossing is the non-radiative conversion to
an electronic state of different multiplicity.
☐ 4. A Jablonski diagram is a schematic diagram showing
the types of non-radiative and radiative transitions that
can occur in molecules.
☐ 5. An additional fate of an electronically excited species is
dissociation.
☐ 6. Internal conversion is a non-radiative conversion to an
electronic state of the same multiplicity.
Brief illustration 11G.3
state laser (Fig. 11G.10). In one form it consists of Nd3+ ions
at low concentration in yttrium aluminium garnet (YAG,
specifically Y3Al5O12), and is then known as an Nd:YAG laser.
the infrared. The most common wavelength of operation is
1064 nm, which corresponds to the electronic transition from
the 4F to the 4I state of the Nd3+ ion.
4
F
1.06 μm
Energy
Pump
4
I
Thermal
decay
Figure 11G.10  The transitions involved in a neodymium laser.
Many of the most important laser systems are solid-state
devices; they are discussed in Topic 15G.
☐ 7. Predissociation is the observation of the effects of dis-
sociation before the dissociation limit is reached.
☐ 8. Laser action is the stimulated emission of coher-
ent radiation between states related by a population
inversion.
☐ 9. A metastable excited state is an excited state with
a long enough lifetime for it to undergo stimulated
emission.
☐ 10. A population inversion is a condition in which the
population of an upper state is greater than that of a
relevant lower state.
☐ 11. Pumping, the stimulation of an absorption with an
external source of intense radiation, is a process by
which a population inversion is created.