Photoacoustic Spectroscopy
The sensitive technique of measuring small absorptions is applied
mainly when minute concentrations of molecular species have to be
detected in the presence of other components at higher pressure.
An example is the detection of spurious pollutant gases in the
atmosphere.
Its basic principle is summarised as:
Fig. 1. Schematic experimental arrangement for opto-acoustic spectroscopy.
A beam of a tunable laser is sent through the absorption cell (Fig. 1).
If the laser is tuned to an absorbing molecular transition → , part of the
molecules in the lower level will be excited into the upper level .
By collisions with other atoms or molecules in the cell, these excited
molecules may transfer their excitation energy ( − ) completely or partly
into translational, rotational or vibrational energy of the collision partners.
At thermal equilibrium, this energy is randomly distributed onto all degrees
of freedom, causing an increase of thermal energy and with it a rise of
temperature and pressure at a constant density in the cell.
With infrared lasers, the molecules are generally excited into higher
vibrational levels of the electronic ground state.
Assuming cross sections of 10 − 10 cm for the collisional
deactivation of vibrationally excited molecules, the equipartition of
energy takes place only about 10 sec at pressures around 1 Torr.
As the spontaneous lifetimes of these excited vibrational levels
~10 − 10 sec, it follows that at pressures above 1 Torr the
excitation energy, absorbed from the laser beam, will be almost
completely transferred into thermal energy.
When the laser is chopped at frequencies below 10 kHz, periodical
pressure variations appear in the absorption cell which can be detected
with a sensitive microphone placed at the inner side of the cell.
The output signal from the microphone is proportional to the absorbed
laser energy, and therefore allows determination of the absorption
coefficient.
Because this method uses the conversion of photon energy into
periodical pressure variations, it is called photoacoustic spectroscopy
and the device is named spectraphone.
The solid sample to be measured is placed in a
sealed vessel to which a microphone is attached.
When a modulated infrared light beam is
absorbed by the sample, heat is generated due
to the incident light.
This heat causes pressure changes in the
surrounding gaseous layer, which can be
detected by the high-sensitivity microphone.
The signals from the microphone are acoustic
interference waves.
Applying Fourier transformation to these signals
produces a spectrum similar to an absorption Fig. 2. Principle of photoacoustic spectroscopy
spectrum.
Photoacoustic spectroscopy (PAS) is based on the detection of
modulated heat release from the absorption of periodically
interrupted electromagnetic radiation by a test sample enclosed in an
air-tight cell generally known as photoacoustic cell (PA cell).
When the molecules/atoms of the test sample are excited by
absorbing the modulated electromagnetic radiation, they may relax to
lower/ground state by two processes:
(i) Radiative decay in which characteristic photons are emitted
(ii) Non-radiative decay in which molecules/atoms of the test sample
relax to lower state by emitting phonons.
Thus the heat, generated by the non-radiative decay of excited states,
diffuses to the sample boundary and causes a thin layer of air/gas near
the surface to expand and contract periodically (Fig. 3).
Fig. 3. Generation of photoacoustic signal in airtight enclosure (Photo Acoustic cell).
The acoustic waves thus formed are usually detected by microphone,
and signal amplitudes and phases are measured by lock-in-amplifier.
The amplitude of the PA signal depends on the modulated light intensity,
the absorption coefficient, the thermal and elastic properties of the
sample and the coupling gas as well as on the modulation frequency,
whereas its phase depends on the time lag caused by molecular
processes and the electronic detection system.
Photoacoustic spectroscopy thus involves irradiating intermittent light
onto a sample and then detecting the periodic temperature fluctuations
in the sample as pressure fluctuations.
Fig. 4. General experimental setup for performing photoacoustic spectroscopy on a gas.
As far as saturation effects can be neglected, the photoacoustic signal
= Δ 1−
The acoustic signal is proportional to
the density of absorbing molecules in level ,
the absorption cross section ,
the path length Δ ,
the incident mean laser power , and
the sensitivity of the microphone.
The signal decreases with increasing quantum efficiency (which gives
the ratio of emitted fluorescence photons to absorbed laser photons)
The factor depends on the spectraphone paranmeters.
Features of PAS
1. Permits measurements without pretreatment, regardless of
sample form
2. Can even be used to measure optically-neutral samples that do
not transmit or reflect incident light
3. Measurement sensitivity increases as the light source intensity
increases
4. Obtains information at different depths
Fig. 5. How photoacoustic spectroscopy can
perform depth profiling.
The commonly accepted mechanism for the photoacoustic effect is called
RG theory, after its developers Rosencwaig and Gersho.
RG theory based on thermal diffusion equations is a well-known theory for
solid samples.
This theory is based on the photoacoustic signal and the three parameters:
sample thickness ,
light absorption length (where = 1/ , → absorption coefficient), and
thermal diffusion length !" (!" = 1/#" , #" → thermal diffusion coefficient)
It is classified according to whether the sample is
optically transparent ( > ) or opaque ( < ),
thermally thick (!" < ) or thermally thin (!" > ).
For an optically transparent sample, the photoacoustic signal reflects the
sample optical properties, regardless of the sample thermal properties.
However, only when the sample is optically opaque and thermally thick
(!" < ), the PA signal is proportional to the sample absorption coefficient
and the thermal diffusion length.
In this case, although the sample is optically opaque, it is said to be
photoacoustically transparent.
Since the thermal diffusion length is a function of the modulation
frequency of the incident light, increasing the modulation frequency and
reducing the thermal diffusion length, such that !" < , makes an
optically opaque sample photoacoustically transparent.
Also, as the PA signal is proportional to the thermal diffusion length for a
thermally thick sample, the depth from which the PA signal is emitted can
be changed by changing the modulation frequency.
In other words, increasing the modulation frequency reduces the depth
and the signal intensity.
For a normal Michelson interferometer, the modulation frequency & is
expressed as & = 2()̅ .
It is dependent on the velocity of the movable mirror (( cm/sec) and the
wavenumber )̅ (cm )
Therefore, & decreases as the movable mirror speed decreases.
Conversely, as the thermal diffusion length increases, information is
obtained from a deeper depth from the surface.
Fig. 7. CO- laser-excited PA spectra of powders of heroin (on the left) and morphine (on right).
Fig. 8. PA spectra of . vapor in the wavelength region 492–552 nm (20,300–18,100 cm ). The
little downward arrow indicates the wavelength of exciting radiation that dissociates I2 into two
iodine atoms (20,043 cm ).
Fig. 9. PAS spectrum for sponge
