LABORATORY EXPERIMENT

pubs.acs.org/jchemeduc

Molecular Iodine Fluorescence Using a Green Helium-Neon Laser

J. Charles Williamson*
Chemistry Department, Willamette University, Salem, Oregon 97301, United States

bS Supporting Information
ABSTRACT: Excitation of molecular iodine vapor with a green (543.4 nm) helium-neon
laser produces a fluorescence spectrum that is well suited for the upper-level undergraduate
physical chemistry laboratory. Application of standard evaluation techniques to the spectrum
yields ground electronic-state molecular parameters in good agreement with literature values.
The use of a green helium-neon laser provides advantages in data collection, data analysis,
cost, and safety relative to other I2 excitation sources.
KEYWORDS: Upper-Division Undergraduate, Physical Chemistry, Laboratory Instruction,
Hands-On Learning/Manipulatives, Fluorescence Spectroscopy, Lasers, UV-VIS Spectros-
copy, Quantum Chemistry

ovibronic spectroscopy between the 3Πþ 1 þ

0u B and Σg X states
R of molecular iodine vapor is a well-recognized experi-
mental platform for reinforcing student comprehension of the
quantum mechanical description of matter, and light-matter
interactions.1-3 Potential-well parameters for the B state are
extracted from analysis of the absorption spectrum, and the X
state is characterized using emission spectrum analysis. Sug-
gested excitation sources for emission spectra in the I2 experi-
ment include the 546.1 nm line of a mercury lamp,4,5 the
632.8 nm (red) helium-neon laser,6-8 the 514.5 nm line of
the argon ion laser,9,10 the 520.8 and 647.1 nm lines of the
krypton ion laser,3 and 532.1 nm output from a frequency-
doubled Nd:YAG laser.3,11 Each of these excitation sources
has strengths and drawbacks in its application to the under-
graduate experiment. For example, the red HeNe I2 fluorescence
is relatively weak and includes overlapping emission from both
the J0 = 32, v0 = 6 and J0 = 128, v0 = 11 states. Relaxation from these
states leads to rotational doublets that can be used to determine the
X-state rotational constant B ~00e and the equilibrium internuclear
00 6,8
distance Re . In comparison, fluorescence following 514.5 nm
Arþ excitation is much stronger than red HeNe I2 laser-induced
fluorescence (LIF), but is generated by two transitions involving small
J00 : P(13) 43-0 and R(15) 43-0. The resulting closely spaced doublet
pairs are not useful for undergraduate rotational analysis, although
students can analyze the anti-Stokes doublet from the weaker R(98)
58-1 transition instead.10 Significant disadvantages of argon ion,
krypton ion, and research-grade Nd:YAG lasers for this experiment
are their costs and the hazards of their high power emission.
Recently, the I2 LIF spectra generated with green (543.4 nm)
and yellow (593.9 nm) HeNe lasers were characterized.12 A
commercial green HeNe laser was found to excite at least six
different molecular iodine rovibronic transitions, although the
LIF spectrum was dominated by relaxation from just one: R(106)
28-0. This spectrum has a number of desirable properties with
respect to the undergraduate I2 fluorescence experiment. An
overview of data collection and analysis is provided in the next
two sections, followed by a summary of the advantages of using a
green HeNe laser for I2 excitation relative to other laser sources.
’ EXPERIMENTAL SECTION
Complete experimental details are presented in the Instructor
Notes in the Supporting Information. Briefly, laser-induced
fluorescence (LIF) was generated from iodine vapor using a
300 μW green HeNe laser (25-LGP-173, Melles Griot). Despite
the low laser power, the orange fluorescence was bright enough
to see by eye in a dimly lit room. The I2 fluorescence was
collected at 90° to laser incidence and detected using a mono-
chromator with photomultiplier tube. Although the output
power of the green HeNe remained constant to better than
1%, the I2 fluorescence clearly cycled in intensity with a period of
a few seconds at first and over several minutes once the laser had
warmed up. Measured fluorescence peaks from the R(106) 28-0
excitation varied in intensity by 50% on a similar time scale, but
all peaks remained present; the spectrum did not evolve through
various emission band structures like Tellinghuisen has reported
for green diode lasers.11 Tellinghuisen proposed that different I2
transitions are accessed over time by diode lasers because the
Published: March 09, 2011

Copyright r 2011 American Chemical Society and

Division of Chemical Education, Inc. 816 dx.doi.org/10.1021/ed100908u | J. Chem. Educ. 2011, 88, 816–818
Journal of Chemical Education
Figure 1. (A) Green HeNe (543.4 nm) LIF spectrum of gas-phase
molecular iodine at 1 nm resolution. The dominant series of emission
peaks comes from J0 = 107, v0 = 28 in the B state. Every fifth vibronic peak
is numbered with its final value of v00 . Small peaks evident below 540 nm
in the 6 magnification are anti-Stokes lines from other excited states.
(B) The 28 f 1 rotational doublet at two levels of resolution (0.25 and
0.034 nm). Smaller peaks in the higher-resolution scan arise from
collision-induced changes in J0 prior to relaxation.
emission wavelength shifts from temperature-dependent changes in
the diode laser cavity. Similar temperature-dependent effects are
likely the source of the intensity fluctuations seen in the green
HeNe I2 fluorescence.
’ HAZARDS
Iodine is toxic and corrosive13 and is best handled in a fume
hood. Most green HeNe lasers are Class IIIa/3R devices and
caution should be exercised to avoid direct exposure of the eye to
the emitted radiation.
’ RESULTS AND DISCUSSION
A low-resolution scan (1 nm) of the green HeNe I2 LIF
spectrum is shown in Figure 1A. At this resolution, the spectrum
consists of a series of peaks corresponding to vibronic v0 = 28 f v00
transitions. Peak numbering begins with v00 = 0 at the laser line.
The observed peak intensity distribution results from both
Franck-Condon overlap and the overall instrument response
as a function of wavelength. Missing peaks in the sequence
correspond to poor Franck-Condon overlap and must be
included in the numbering scheme (such as v00 = 4). Several
small peaks seen to the blue of the laser line are due to anti-Stokes
emission from other I2 transitions accessed by the green HeNe
laser.12
817
LABORATORY EXPERIMENT
Figure 2. Representative rovibronic energy diagram for 28 f 1
relaxation of molecular iodine following excitation of the R(106) 28-0
transition with a green HeNe laser. Before relaxation, some collisions
transfer B-state population in J0 = 107, v0 = 28 into other rotational levels,
such as J0 = 105 or 109.
At higher resolution, each vibronic peak resolves into a
rotational doublet (Figure 1B). Iodine follows the ΔJ = (1
selection rule, and molecules put into the J0 = 107,v0 = 28 state by
green HeNe laser excitation relax back to either J00 = 106 (net
ΔJ = 0) or with a lower energy photon, J00 = 108 (net ΔJ = þ2).
Figure 2 presents an energy diagram for this process.
Determination of the X-state vibronic parameters from LIF
data has been described in this Journal,10,14 and details are
presented in the accompanying Instructor Notes in the Support-
ing Information. Briefly, students calculate the energy difference
Δν~0 between the laser photon energy and the ΔJ = 0 peak of each
doublet. The coefficients of the vibrational term value polyno-
mial G ~00 (v00 ) are derived by fitting Δν
~0 as a function of v00 þ (1/2).
Our students typically find that a third-order polynomial fit is
statistically justified by the uncertainty and span of their data, and
thus, they determine the parameters ν~00e , ν~00e x00e , and ν ~00e y00e in the
~ 00 00
expansion of G (v ). Students obtain excellent agreement with
the literature value for ν~00e (Table 1), although their values are
systematically low by ≈1.3 cm-1 due to an approximation in the
analysis that is explained further in the Instructor Notes in the
Supporting Information. Students obtain good agreement for
ν~00e x00e , and qualitative agreement for ν~00e y00e . The spectroscopic
dissociation energy of the X-state potential well, D ~ 000 , is found
from extrapolation of Δν~0 to its maximum value. The value of D ~ 000
is typically overestimated by several hundred wavenumbers in
this treatment (Table 1). This error is unavoidable given the
number of vibronic peaks our students can observe.10 Better
agreement would be found by measuring peak energies to higher
v00 , but the sensitivity of our detection scheme cuts off at about
860 nm.
dx.doi.org/10.1021/ed100908u |J. Chem. Educ. 2011, 88, 816–818
Journal of Chemical Education LABORATORY EXPERIMENT

Table 1. Molecular Iodine X-State and B-State Potential peaks, and v00max with our instrumentation is 20 for red HeNe
Energy Parameters Determined by the Green HeNe LIF excitation, 36 for green HeNe excitation, and 42 for 514.5 nm
Experiment Arþ excitation. The latter laser is a superior choice in this regard.
However, the green HeNe laser is an order of magnitude less
Quantity Literaturea This Workb
expensive than an argon ion laser, safer to operate, and produces
X State a simpler emission spectrum with rotational structure that is
ν00e /cm-1
~ 214.53 213.0 ( 0.3 easier to resolve.
ν00e x00e /cm-1
~ 0.6130 0.580 ( 0.022
ν00e y00e /cm-1
~ -1.03  10-4 (-2.4 ( 0.4)  10-3
~ 000 /cm-1
D 12440.2 (1.310 ( 0.027)  104 ’ ASSOCIATED CONTENT
~ 00e /cm-1
D
~00e /cm-1
B
12547.3
0.037368
(1.321 ( 0.027)  104
0.0373 ( 0.0006
bS Supporting Information
Notes for instructors; representative data; student guidelines
R00e /pm 266.64 266.8 ( 2.2 for data analysis. This material is available via the Internet at
http://pubs.acs.org.
B State
~0 (v0 =28)/cm-1
B 0.023374 0.0231 ( 0.0006
a
Data from refs 15-17. b The vibronic peak series in the fluorescence ’ AUTHOR INFORMATION
data terminated at v00max = 36. The peak location data were fit to a third-
order polynomial. Uncertainties are expressed at the 95% Corresponding Author
confidence level. *E-mail: jcwillia@willamette.edu.

Rotational analysis of the I2 LIF spectrum has also been

described before.6-8,10 As seen in Figure 2, the two transitions
that lead to a particular rotational doublet originate from the
same excited state, and thus, the energy difference Δν ~D between
the doublet peaks is equal to the spacing between the J00 and
J00 þ 2 levels in the X state. Ignoring centrifugal distortion, this
spacing is
~00 ðv00 Þ
ΔνD ¼ ð4J 00 þ 6ÞB
~00 (v00 ) is
where to first order B
 
B ~00e - Re 00 v00 þ 1
~00 ðv00 Þ ¼ B
2 668.
Equation 2 features the fundamental rotational constant B ~00e and
the vibration-rotation coupling constant R00e . If students analyze
the v0 = 28 f v00 = 1 doublet spacing, the approximation that B ~00e
~ 00 00
equals B (v = 1) introduces an error of only 1%. The 16
equilibrium internuclear distance of the X state, R00e , is then
calculated from B ~00e in the usual away, and students have the
parameters they need to calculate an X-state Morse potential.10
Students can also determine R00e from the spectrum by measuring
the spacings of many rotational doublets.6 Observant students
may notice the presence of satellite peaks in a high-resolution
doublet spectrum (Figure 1B). These peaks arise from collision-
induced changes in the rotational state of excited I2 prior to
relaxation to the X state;18 in this case, ΔJ equals integer
multiples of two (Figure 2).
’ SUMMARY
Undergraduate analysis of the molecular iodine laser-induced
fluorescence spectrum generated with a green HeNe laser yields
X-state potential parameters with good accuracy. The fluores-
cence emission is stronger per milliwatt of excitation than that
from other laser sources,12 including the argon ion, and the
spectrum is dominated by emission from just a single rovibra-
tional level in the B-state, J0 = 107,v0 = 28. This large value for J0
leads to widely spaced emission doublets suitable for rotational
analysis. The accuracy to which the X-state electronic well depth
can be determined depends on the number of observed vibronic
’ ACKNOWLEDGMENT
The author thanks David Goodney and the Willamette
University students enrolled in the Experimental Chemistry I
course during 2009 and 2010. This work was supported by a
Willamette University Atkinson Grant.
ð1Þ
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