You are on page 1of 6

Fast measurement of the refractive-index dispersion of dilute liquid

solutions of absorbing molecules


Elizareth Hernández-Sánchez, Humberto Contreras-Tello, Celia Sánchez-Pérez,
Augusto García-Valenzuela
Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de
México, Apartado Postal 70-186, Distrito Federal 04510, México;

ABSTRACT

We describe a fast method for measuring the refractive-index dispersion of transparent and absorbing liquid solutions.
The method is based on measuring the reflectance spectra of an optical beam of white light in an internal reflection
configuration near the critical angle defined by the refractive indices of the incident medium (a glass prism) and that of
the solvent, which is assumed to be transparent. From a few reflectance spectra taken near the critical angle with the pure
solvent and the solution, the dispersion of the contribution to the refractive index of the solute (the sample) can be
obtained. We present results with solutions of Rodamine 6G dissolved in distilled water and in methanol showing the
feasibility of the proposed method.
Keywords: Refractive-Index Dispersion, Anomalous Dispersion, Reflectance Spectra, Internal Reflection, Critical
Angle

1. INTRODUCTION
A molecule in solution contributes to the refractive index through its molecular polarizability which relates the electric
dipolar moment acquired by the molecule with the local electric field felt by the molecule. The polarizability is in
general a complex quantity. Its imaginary part is related to the dissipation of electromagnetic energy. Both, the real and
imaginary parts of the molecular polarizability are functions of the frequency of the electromagnetic wave. These
functions give valuable information of the molecule and its interaction with the surroundings (the solvent) (see for
example Ref. [1]). We will refer to the contribution to the refractive index of a solution of the molecular species of
interest as the refractive index difference. Measuring the spectrum of imaginary part of the refractive index difference
for a given molecule is relatively straight forward. It requires measuring the absorption of light as a function of
wavelength. One can use, for instance, a rectangular cell filled with the solution and measure the transmittance spectra at
normal incidence. After a few precautions to remove from the measurement the effect of the interfaces of the cell one
may readily obtain the imaginary part of the refractive index difference using Beer-Lambert’s law. Measuring the real
part of the refractive index difference is, however, not so straight forward. To this end one needs a spectroscopic
refractometer. However, such instruments are not well developed to date. On may find in the market highly accurate
refractometers that measure at one or at a few wavelengths only. Novel experimental setups improving over commercial
instruments have been reported in the past years (see for example Refs. [2,3]). However, these improvements are also
suitable for measuring at a single or at a few discrete values of the wavelength of light. In this work we propose and
study a variation of the method described in Ref. [3] which is suitable for fast spectroscopic measurement of the real part
of the refractive index change of solutions of complex molecules.

2. THEORY
The aim of the technique we propose here is to measure rapidly the refractivity of a sample molecule in solution.
Basically one needs to measure the difference between the refractive index of a dilute solution of the molecule of interest
in a given solvent and the refractive index of the pure solvent as a function of wavelength.
2.1 Optical beam reflection in an internal reflection configuration
The proposed method assumes an optical beam incident to a flat interface between two linear, isotropic, non-magnetic
and homogeneous media. The incidence medium is assumed to be have a higher refractive index (n1) than the external

Seventh Symposium Optics in Industry, edited by Guillermo García Torales, Jorge L. Flores Núñez, Gilberto Gómez Rosas,
Eric Rosas, Proc. of SPIE Vol. 7499, 74990E · © 2009 SPIE · CCC code: 0277-786X/09/$18 · doi: 10.1117/12.851114

Proc. of SPIE Vol. 7499 74990E-1


medium (n2), that is, we assume an internal reflection configuration (n1 > n2). Thus, in the absence of optical absorption
of the external media, that is if Im(n2) = 0, there is a well defined critical angle given by sin-1(n2/n1). The reflectance of a
TE or a TM polarized plane-wave at the interface is given by,
2 2
n1 cos θi − n2 1 − ( n1 n2 ) sin 2 θi n2 cos θi − n1 1 − ( n1 n2 ) sin 2 θi
2 2

RTE = and RTM = (1)


n1 cos θi + n2 1 − ( n1 n2 ) sin θi n2 cos θi + n1 1 − ( n1 n2 ) sin 2 θi
2 2 2

For unpolarized light the reflectance is given by a weighted average of the above expressions. In practice however, one
measures the reflectance of an optical beam with finite width and angular divergence. For simplicity let us assume a
Gaussian beam. In this case the reflectance is given by [4],
π/ 2
kw w2 k 2

2
R= exp[− (θ − θi ) 2 ] F (θ) d θ , (2)
2π 0 2

where w is the beam’s waist radius, k = 2π/λ is the wave number and F (θ) is the weighted-average of the Fresnel
reflectance formulas given above accordingly to the polarization of the incident wave. For instance, if the light is
completely unpolarized when it reaches the interface we have that F (θ) = 12 RTE + 12 RTM , otherwise the case-specific
average must be taken.
2.2 Change of the reflectance due to a refractive index change of the external medium
The curve of reflectance versus the angle of incidence for an interface between two transparent media in an internal-
reflection configuration changes rapidly just before the critical angle. Just after the critical angle the reflectance reaches
unity and remains constant thereafter. Actually, for a plane wave the angle-derivative of the reflectance tends to infinity
as the angle of incidence approaches the critical angle from smaller angles and is identically zero for angles of incidence
above the critical angle. Therefore there is an infinite discontinuity in the angle derivative of the reflectance of a plane
wave at the critical angle. As mentioned before, in practice one has an optical beam of finite width and angular
diffraction, and not idealized plane wave. For an optical beam, the discontinuity disappears and a sharp maximum of the
angle derivative near the critical angle is found [5]. Nevertheless, the reflectance near the critical angle is highly
sensitive to changes in the angle of incidence and also to changes in the refractive index of either the external
(transmission) or internal (incidence) medium. Let us consider the refractive index of the external media is the refractive
index of the solvent, ns, plus a small contribution of the sample which is in general a complex number, δn = δn’ + iδn’’.
Then we write,
n2 = ns + δn '+ iδn '' . (3)

The reflectance at any given angle of incidence will change when we add the solute to the solvent, by ΔR. If the change
in refractive index is small we may write,
ΔR ≈ DR δn '+ DI δn '' , (4)

where DR = ⎡⎣∂R ∂n2' ⎤⎦ is the partial derivative of the reflectance with respect to the real part of the refractive index of
n2 = ns

the external medium evaluated at n2 = ns and DI = ⎡⎣∂R ∂n2'' ⎤⎦ is the partial derivative with respect to the imaginary
n2 = ns

part also evaluated at n2 = ns. Now, for angles of incidence near the critical angle, ∂R ∂n2' and ∂R ∂n2'' , are strong
functions of the refractive indices, n1 and n2 and of the angle of incidence. In Figure 1 we plot D these functions
evaluated at n2 = ns. Assuming a n1 of a BK7 glass and n2 that of distilled water at the wavelength of λ = 404.7 nm and
λ= 706.5 nm.
We can appreciate in Fig. 1 (a) that DI is practically zero for angles of incidence below the critical angle and non-zero
for angles of incidence above the critical angle. For DR we have the opposite. Therefore, for angles of incidence below
the critical angle we may write,
ΔR (θi < θc ) ≈ DR δn ' , (5)

Proc. of SPIE Vol. 7499 74990E-2


(a) (b)
0 0
404.7 nm TE polarization 706.5 nm
TE polarization 706.5 nm 404.7 nm
-10 -10 w = 100 μm
w = 100 μm
-20 -20

DI
DR

-30 -30
minimum at - 200 minimum at -210

-40 -40

-50 -50
48 50 52 54 56 58 60 62 64 66 50 52 54 56 58 60 62 64 66
Angle of incidence (deg.) Angle of incidence (deg.)

Fig.1: Plot of the derivatives of the reflectance with respect to a)δn’ and b)δn’’ versus the angle of incidence for TE
polarization and for BK7 glass as the incidence medium and water as the transmission medium for two wavelengths:
λ = 706.5 nm and λ = 404.5 nm. We assumed a gaussian beam of waist radius of w = 100 μm.

Now, the refractive indices n1, n2 and δn are all functions of the wavelength. Thus, R and DR are functions of the
wavelength and of the angle of incidence: R = R (λ, θi ) and DR = DR (λ, θi ) .

Clearly, if we know DR at a given angle of incidence we can measure ΔR (λ) and obtain Δn2 (λ) from Eq. (5).
However, near the critical angle DR is a strong function of θi and λ, and due to small variations in the refractive indices
of the solvent we can not have a good and reliable apriori approximation. On the other hand, measuring DR at a given
angle of incidence would not be practical. Fortunately, we have that near the critical angle the derivative with respect to
the real part of the refractive index of the external medium is nearly proportional to the angle derivative of the
reflectance: ∂R ∂θi . The factor relating the two derivatives is not a strong function of the refractive indices, and
therefore a measurement of the ∂R ∂θi can give us a good estimate of DR . That is we may write,

∂R
≈ β(λ, θi ) DR . (6)
∂θi

In Fig. 2 we plot the factor β(λ, θi ) versus the angle of incidence for TE and TM polarization. The graphs in Fig. 2 were
calculated assuming an incidence Gaussian beam of waist radius of w = 100λ where λ is the wavelength of radiation in
vacuum and the internal and external media was supposed to be BK7 glass and water respectively. The graphs in Fig. 2
show that, at least for the BK7 glass – water interface, the factor β is indeed a smooth function of the angle of incidence
and is nearly insensitive to the wavelength in the visible range.
TE polarization TM polarization
0.0 0.0
w = 100 μm 706.5nm
404.7nm
w = 100 μm 706.5 nm
404.7 nm
-0.2 -0.2

-0.4 -0.4
β

-0.6 -0.6

-0.8 -0.8

-1.0 -1.0
50 52 54 56 58 60 50 52 54 56 58 60
Angle of incidence (deg.) Angle of incidence (deg.)

Fig. 2: Graphs of the factor β defined in Eq. (6) versus the angle of incidence for two different wavelengths, 706.5 nm and
404.7 nm, for (a) TE and (b) TM polarization. The medium of incidence is assumed to be BK7 glass and the external
medium is assumed to be water. We assumed a gaussian beam of waist radius of w = 100 μm.

Proc. of SPIE Vol. 7499 74990E-3


Thus in the case of dilute solutions, we may readily relate a difference in reflectance with a difference in refractive
index. From Eqs. (5) and (6) we obtain,
ΔR
δn ' = β . (7)
∂R ∂θi

2.3 Measuring the refractive index difference due to a molecule in solution


The method we propose here for measuring the refractive index difference between a dilute solution of a given molecule
and that of the pure solvent consists of measuring the reflectance difference ΔR and ∂R ∂θi in an internal reflection
configuration at a given angle of incidence θi. Then, we may calculate the factor β defined in Eq. (6) using the Fresnel
formulae and Eq. (2). We assume we know the refractive indices of the incidence medium (an optical prism) and of the
solvent. Finally, we use Eq. (7) to obtain the refractive index difference between the solution of interest and the solvent.
Note that ∂R ∂θi should be measured with the solvent as the external medium. The measurement of ∂R ∂θi requires of
measuring the reflectance at a few angles of incidence around the critical angle θc. ΔR is obtained by subtracting from
the reflectance of the solution the reflectance of the solvent. Both measurements made at the same angle of incidence θi.
Measuring ΔR requires two reflectance measurements only. This procedure may be carried out simultaneously at many
wavelengths within a specific range using a beam of white light and a spectrophotometer as described in the next
section.

3. EXPERIMENTAL SETUP
We assembled the experimental setup shown in Fig. 3 for the spectral measurement of the reflectance of a polychromatic
beam that reflects in the base of a BK-7 glass prism in contact with the solution to be characterized. A collimated beam
with a divergence angle of 2.2° is obtained from an halogen lamp pigtailed to an optical fiber of 600 μm core diameter
with a conventional optical collimator in its end. This divergent beam illuminates the entrance face of the prism and
reflects into its base put in contact with a container in which is injected the solution or the solvent. The output beam is
focused by a lens. The lens is used to directly convert angle position into linear position. To obtain the reflectance as a
function of the incidence angle, a 100 μm core diameter fiber is placed at the focal plane of the lens. The fiber brings the
captured light to a spectrophotometer. A spectrum is measured at different positions along an horizontal line across the
focal plane. The incident beam illuminates an angular cone 2.2o wide around the critical angle, so the reflectance can be
obtained at different angles θi within this range by measuring the transmission spectra at the corresponding positions
along the focal plane of the lens.
x Output Spectrophotometer
optical fiber
Input Linear
y z optical fiber stage
Halogen
lamp

Prism x
Collimator
Lens
Computer

Sample

θ
Goniometer

Fig. 3 Schematic of the spectroscopic refractometer setup.

Proc. of SPIE Vol. 7499 74990E-4


The performed experiments consisted of filling the prism with solvent and take the spectra of the reflected light at two
angular positions near the dark edge defining the critical angle zone. We refer to the critical zone as the zone around the
inflection point on the reflectance curves. The inflection point separates the transition from low reflectance to high
reflectance regions. Next the solvent in the container is replaced by the suspension and the reflectance spectra are taken
at the same angular positions. The term ∂R ∂θi at each wavelength is experimentally obtained by estimating the slope
of the reflectance from these measurements. For obtaining reflectance versus the angle of incidence curves the fiber is
displaced at steps of 50 μm across the output beam, registering the spectrum at each position. From the measured spectra
at the different angular positions, the reflectance curve for each wavelength is extracted.

4. EXPERIMENTAL RESULTS
In Fig. 4 we show the graphs of the reflectance as a function of the angle of incidence for the distilled water and the
methanol used as the solvents. Each curve is for a different wavelength. We plot curves from 460nm and 600 nm. It can
be seen that the critical angle zone is well defined. For the water the critical angle value is obtained at around 61.2° and
for methanol this value is around 60.6°. The displacement between the curves for the different wavelengths indicates the
dispersion of ns .

(a) (b)
1.0 1.0

0.9 0.9

0.8 0.8

Reflectance
Reflectance

0.7 0.7

0.6 0.6

0.5 0.5

0.4 0.4
59.4 59.6 59.8 60.0 60.2 60.4 60.6 60.8 61.0 60.2 60.4 60.6 60.8 61.0 61.2 61.4 61.6
Angle of incidence (deg.) Angle of incidence (deg.)

Fig.4 Graphs of reflectance versus the angle of incidence for: (a) methanol and (b) distilled water used as a solvent.
We measured the reflectance versus angle of incidence of the rhodamine 6G diluted in methanol at two concentrations of
0.0001 M and 0.001M. The graphs are shown in Fig. 5. In these cases the critical angle for the concentration of 0.001M
is less sharp. The horizontal shift between the curves for different wavelengths is bigger than that in Fig. 5(a) meaning
that the solution has a greater dispersion in δn’. Moreover the curves are smoothed and there is no well defined critical
angle at many wavelengths because the solution is strongly absorbing at those wavelengths (indicating a large imaginary
part of the refractive index at that wavelength).

(a) (b)
1.0 1.0

0.9 0.9

0.8 0.8
Reflectance
Reflectance

0.7 0.7

0.6 0.6

0.5 0.5

0.4 0.4

0.3 0.3
59.4 59.6 59.8 60.0 60.2 60.4 60.6 60.8 61.0 59.6 59.8 60.0 60.2 60.4 60.6 60.8 61.0 61.2 61.4
Angle of incidence (deg.) Angle of incidence (deg.)

Fig. 5 Reflectance versus the angle of incidence of rhodamine 6G diluted in methanol for (a) 0.0001M and (b) 0.001M.

Proc. of SPIE Vol. 7499 74990E-5


In Fig. 6 (a) and (b) we plot the values of the dispersion of the real part of the refractive index increment (δn’) produced
by the rhodamine 6G in a concentration of 0.01M in methanol and distilled water respectively. These curves were
calculated using Eq. (7) above with data taken from the corresponding reflectance spectra. In Fig. 6(a) the absorption
band centered at 544 nm is very closed (~ 4nm) to that reported by Leupacher et al [6] obtained with a similar spectral
technique. Also the maximum value of δn’ = 10x10-3 is in good agreement. Indeed the spectral regions sideways the
absorption band are less defined so we need to improve the accuracy of our method. In the case of the solution in
distilled water Fig. 6(b) the absorption band is extended over a wide spectral band and the δn’ dispersion differs from
that measured in methanol. This is probably due to the presence of aggregates in the solution as reported by Toptygin
et al [7] that means that the Rhodamine 6G molecule interacts in a different way in water.

(a) (b)
10 10

9 9
8
8
7

-3
-3

δn' x 10
δn' x10

6
5 6

4
5
3
4
2
1 3
460 480 500 520 540 560 580 600 460 480 500 520 540 560 580 600
W avelength (nm ) Wavelength (nm)

Fig. 6 Refractive index dispersion δn’ for a solution of 0.01 M of rhodamine 6G diluted in
(a) methanol and (b) distilled water

DISCUSSION

We proposed a technique to determine the dispersion of the real part of the refractive index of absorbing liquids. The
method is based in the measurement of a few reflection spectra near the inflexion point near of the reflectance curve in
an internal reflection configuration. We experimentally validate the principle of measurement and present results for the
dispersion of the refractive index increment of Rhodamine 6G solutions in a wavelength range around an absorption
band.
Acknowledgments
We acknowledge financial support from Dirección General de Asuntos del Personal Académico from Universidad
Nacional Autónoma de México through Project IN120309.

REFERENCES
[1]
M. E. Baur, D. A. Horsma, C. M. Knobler, and P. Pérez, “Dielectric constant and refractive index of weak complexes in
solution” J. Phys. Chem. 73 (3), 641-650 (1969).
[2]
M. L. Eickhoff, J. L. Hall, “Real-time precision refractometry: new approaches”, Appl. Opt. 36 (6), 1223-1234 (1997).
[3]
Michael McClimans, Charles LaPlante, David Bonner, and Samir Bali, “Real-time differential refractometry without
interferometry at a sensitivity level of 10-6”, Applied Optics 45 (25), 6477-6486 (2006).
[4]
A. García-Valenzuela, M. C. Peña-Gomar, J. Villatoro, “Sensitivity analysis of angle-sensitive-detectors based on a film
resonator”, Opt. Eng. 42 (4), 1084-1092 (2003).
[5]
A. García-Valenzuela, Mary Carmen Peña-Gomar, C. Fajardo Lira, “Measuring and sensing a complex index of refraction by
laser reflection near the critical angle”, Opt. Eng. 41 (7), 1704-1716 (2002).
[6]
W. Leupacher and A. Penzkofer, “Refractive-index measurement of absorbing condensed media”, Appl. Opt. 23 (10), 1554-1557
(1984).
[7]
D. Toptygin, B. Z. Packard and L. Brand, “Resolution of absorption spectra of rhodamine 6G aggregates in aqueous solution
using the law of mass action”, Chemical Physics Letters, 277, 430-435 (1997).

Proc. of SPIE Vol. 7499 74990E-6

You might also like