ATR Theory

Under certain conditions, radiant energy incident on an internal Wavelength of Infrared Radiation
surface of a transparent material with a high refractive index is The penetration depth of the infrared energy into the sample is
totally reflected. When an infrared absorbing material is in optical wavelength dependent. As the wavelength of the infrared radiation
contact with a totally internally reflecting surface, the intensity of increases, the depth of penetration increases. It is often convenient
the internally reflected radiation is diminished for those wavelengths to discuss this in terms of wavenumber: the depth of penetration
where the material absorbs energy. Since an internal reflecting increases as the wavenumber decreases. This causes the relative
surface is essentially a perfect mirror, the attenuation of this band intensities in the ATR spectrum to increase with decreasing
reflected intensity by a material on its surface provides a means wavenumber when compared to a transmission spectrum of the
of producing its absorption spectrum. Such spectra are called same sample. This phenomenon can be mathematically corrected
internal reflection spectra or attenuated total reflection (ATR) by most commercial FT-IR software packages.
spectra. ATR is the most common term for this spectral collection
technique. It is convenient to regard the process as internal Refractive Index
reflection and the data as ATR spectra. The high index of refraction The refractive index of the IRE has the following two effects on
material used to create internal reflection is called an internal the ATR spectrum obtained:
reflection element (IRE) or an ATR crystal. Both terms are common.
1. By increasing the refractive index of the IRE material, the critical
Figure 1 illustrates the general features of an internal reflection
angle θc is decreased. The critical angle is a function of the
configuration and labeling of various components.
refractive indices of the sample and ATR crystal and is
defined as:

where:
n1 = refractive index of the ATR crystal
n2 = refractive index of the sample
θc = critical angle
2. The refractive index affects the depth of penetration of the
evanescent wave into the sample. By increasing the refractive
Figure 1 index of the IRE, the depth of penetration will decrease (i.e.
changing from ZnSe to Ge). This will decrease the effective
The attenuation of the internally reflected radiation results pathlength and therefore decrease the absorbance of the
from the penetration of the electro-magnetic radiation field into spectrum. High index ATR crystals are needed when analyzing
the matter in contact with the reflecting surface. This field is high index materials.
described as an evanescent wave. It is the interaction of the
evanescent field with the matter in contact with the IRE interface Depth of Penetration
that results in attenuation of the internal reflection. One of the most Control of depth of penetration is obtained by altering the angle
useful characteristics of this field is that its strength decreases of incidence of the incoming IR beam with respect to the crystal
rapidly with increasing depth of penetration into the material. or changing the refractive index of the crystal. The depth of
In general, the depth of penetration is such that ATR spectra can penetration, dp, is a useful qualitative indicator of how far the
be easily collected on thick and/or optically dense samples. evanescent wave extends into the sample. It is the distance from
the crystal-sample interface at which the intensity of the evanescent
Factors Affecting ATR Spectral Analysis wave has decayed to 1/e (approximately 37%) of its original value.
The following factors affect the results obtained in an Depth of penetration is determined using the following formula:
ATR experiment:
• Wavelength of infrared radiation
• Refractive index of the IRE and sample
• Depth of penetration
• Effective pathlength where:
• Angle of incidence λ0 = wavelength of the infrared radiation in vacuum
• Efficiency of sample contact n1 = refractive index of the ATR crystal
• ATR crystal material n2 = refractive index of the sample
θ1 = angle of incidence (see Angle of Incidence later in
this section)

w w w. t h e r m o . c o m 1 . 8 0 0 . 5 3 2 . 4 7 5 2
 REFERENCE MATERIALS

If the calculation takes into consideration the total interaction For horizontal ATR, the sample is applied to only one side of
of the sample with the electric field, the reflected field amplitudes the IRE. To calculate the number of useful reflections, divide N by
are different for perpendicular and parallel polarization when the 2 and round down. For example, if N = 5, 5/2 = 2.5, so there are
incident amplitudes are equal. The effective penetrations (de) are two reflections at the sample for an HATR crystal. The EPL is
mathematically different for the two polarizations. The relative directly related to the absorbance, in that an increase in either
effective penetrations (de⊥, de⎥⎥) for an isotropic medium for the effective penetration or the number of reflections will
perpendicular and parallel polarizations are: increase the measured absorbance.

Angle of Incidence
Changes in the angle of incidence of the infrared radiation have
three effects on the ATR spectrum. The first is that an angle of
incidence must be chosen to exceed the critical angle in order to
have internal reflection and produce an ATR spectrum. In multiple
where: internal reflection, the angle of incidence affects the number of
λ1= wavelength of infrared radiation in the IRE (λ0/n1) reflections, which, in turn, affects the infrared absorbance. As
n1= refractive index of the IRE the angle of incidence increases, the number of reflections
n2= refractive index of the sample decreases and the absorbance decreases. Finally, changing the
θ = angle of incidence (always measured from the normal angle of incidence changes the depth of penetration. When the
to the reflecting surface) angle of incidence is increased, the depth of penetration
The values in the ATR Calculations table below are the decreases so the absorbance will decrease.
average of the values for parallel and perpendicular polarization, i.e.:
Efficiency of Sample Contact
Another factor that affects the quality of an ATR spectrum is the
efficiency of sample contact. Because the evanescent wave
The depth of penetration (as calculated above) is useful for decays very rapidly with distance from the surface, it is important
comparing the effects of the IRE refractive index, the angle of to have the sample in intimate optical contact with the crystal.
incidence and the state of polarization. However, the experimental This is easily achieved with liquids because they wet the surface
sampling depth is two to three times the theoretical depth of of the ATR crystal. For solids, it is important to use a device that
penetration. presses the sample against the IRE.

Effective Pathlength for Multiple Reflections IRE Crystal Material

The effective pathlength (EPL) can be used as an approximate The IRE material defines its refractive index, the infrared
comparison between the expected absorbance of an ATR transmission range, and the chemical properties of the crystal.
spectrum and a transmission spectrum. In a spectrum obtained A crystal material must have a higher index of refraction than the
by transmission, the pathlength is the thickness of the sample sample to allow internal reflection. Materials with a refractive
that is directly related to the absorbance. In ATR, the effective index greater than 2.2 are normally chosen as ATR crystals. An
pathlength is calculated as: ATR crystal material should also be chosen for its chemical
resistance to the sample. ZnSe (n = 2.4), the most common IRE,
EPL = effective penetration X number of reflections (N)
can be used for samples with pH between 5 and 9. AMTIR and
where:
Ge are recommended for use with acids. Either ZnS or Ge is the
N = _____
1
recommended choice for use with bases. However, Ge has high
t tanθ
reflection losses and lower throughput than ZnS, while ZnS has
l = length of crystal
a limited spectral range. See page 89 for additional crystal
t = thickness of crystal
material information.
θ = angle of incidence

ATR Calculations
θ # of reflections (HATR) ZnSe (n1 = 2.4) Ge (n1 = 4) AMTIR (n1 = 2.5)
dp EP EPL(µm) dp EP EPL(µm) dp EP EPL(µm)
30 21 N/A N/A N/A 1.2 0.842 17.68 N/A N/A N/A
40 14 4.4 3.26 45.64 0.763 0.303 4.24 2.76 1.845 38.75
45 12 2.0 1.01 12.12 0.664 0.216 2.59 1.70 0.807 9.68
50 10 1.5 0.582 5.82 0.596 0.162 1.62 1.34 0.493 4.93
55 8 1.25 0.389 3.11 0.547 0.124 .992 1.14 0.339 2.71
60 7 1.11 0.277 1.94 0.510 0.096 .672 1.02 0.245 1.72
θc N/A N/A 38.68 N/A N/A 22.02 N/A N/A 36.87 N/A
Note: n2 = 1.5 @ 1000 cm-1 129