Research: Science and Education
Solvatochromism and Barochromism
Revisited and Revealed
Satoshi Hirayama
Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606, Japan
Ronald P. Steer*
Department of Chemistry, University of Saskatchewan, Saskatoon SK, Canada S7N 5C9; *ron.steer@usask.ca
Most spectra are taken on samples in a condensed phase
where the influence of the surrounding medium on the spec-
tra is unavoidable. The topic of solvatochromism—the effect
of the nature and properties of the solvent on the energies
(and intensities) of spectroscopic transitions of the solute—is
therefore an important one. Nevertheless, if presented at all,
solvatochromism is often treated in a rather qualitative way in
physical and analytical spectroscopy courses. The result is a short
discussion in the classroom of the hypsochromic shifts (to higher
energies, shorter wavelengths) or bathochromic shifts (to lower
energies, longer wavelengths) of resolved features in absorption
spectra caused by the use of more-or-less strongly interacting
solvents. Nevertheless, some useful undergraduate experiments
based on the UV–vis solvatochromism of zwitterionic solutes,
where dipolar solute–solvent interactions dominate, have been
described recently in this Journal (1, 2).
 Ou , l gas
The more general subject of intermolecular interactions is
often presented in some detail in undergraduate physical chem-
istry texts. Quantitative descriptions of dipole–dipole, dipole–
induced-dipole and induced-dipole–induced-dipole (dispersive
 Nl 2 f1 (1)
or London) interactions based on a simple (e.g., point dipole)
model are common. However, the discussion usually is framed
f
in the context of a qualitative description of the molecular basis
for the properties of materials (e.g., real gas behavior), and no
f u l 2
reference is made to direct experimental measurement of the
physical phenomena involved.
Solvatochromism involves a particular application of the
theory of intermolecular interactions in which one of the spe-
cies (the light-absorbing solute molecule) is promoted from an
initial (often ground) state to a second state of higher energy
(i.e., by radiative coupling). The measured solvatochromism
(or solvatochromic shift) is therefore directly related to the dif-
ference in the properties of the solvated solute molecule in the
two radiatively coupled states. By convention, this difference
is taken as the property of the upper state, u, minus that of the
lower state, l.
A complete description of the solvatochromic effects on
electronic spectra is complicated and is therefore not often
included in the standard undergraduate university chemistry
curriculum. Nevertheless, solvatochromism presents the distinct
advantage of being easily demonstrated in the laboratory. We
therefore believe that studies of solvatochromism and baro-
chromism (pressure-induced shifts) provide an opportunity to
illustrate the important physical chemistry of solute–solvent
interactions. In the following paragraphs we introduce a
simplified treatment of the theory of solvatochromism and
barochromism in electronic spectra that is appropriate for pre-
sentation to undergraduates and may help instructors embrace
this opportunity.
© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 2  February 2008  •  Journal of Chemical Education
Theory of Solvatochromism: A Simplified Approach
The basic theory of solvatochromism, attributed to Bayliss
and McRae (3–5), was developed in the mid-1950s and has
stood the test of time. Using second-order perturbation theory
and the point dipole approximation, McRae (5) derived a gen-
eral four-term expression for the electronic transition energies
of a solute embedded inside a spherical cavity of radius r in the
solvent. The solvent is described as a continuum characterized by
its refractive index, n, and its dielectric constant, D (also called
the relative permittivity). Simplifying McRae’s expression by iso-
lating the dipole moment (μ) and polarizability (α) of the solute
and retaining the solvent continuum parameters we obtain eq 1
for the solvent-induced shift of the electronic transition energy,
∆νu, l , in wavenumber (cm‒1) units,
%Ou , l  Ou, l solution
 C1 B u  B l f 1
 C2 N u
2
 C3 Nl N  N
u l 2
 C4 Nl 2 B  B
2
where f1 = (n2 − 1)∙(2n2 + 1) ≥ 0; f2 = (D − 1)∙(D + 2) − (n2 −
1)∙(n2 + 2) ≥ 0; l and u designate the lower and upper states of
the electronic transition, respectively; and C1, C2, C3, and C4 are
all positive constants. (Note that, if so desired, the solute cavity
radius, r, could also be factored out of each of the terms in eq 1;
C1 = C1′r ‒3, C2 = C2′r ‒3, C3 = C3′r ‒3, and C4 = C4′r ‒6.) Each of
the four terms represents a contribution to the solvatochromism
resulting from one combination of dispersive and static dipolar
solute–solvent interactions. The frequency dependence of the
refractive index �������������������������������������������������
of the solvent ����������������������������������
and the polarizability �����������
of the sol-
ute is ignored in eq 1, but this is not a serious omission for the
solvatochromism associated with electronic transitions of solutes
in transparent solvents.
The first term in McRae's four-term derivation of ∆νu, l
has proved difficult to interpret (6). In McRae’s treatment, this
term contains the oscillator strength of the transition (i.e., the
electronic transition moment), but we have recently shown (7)
that it may be reduced to the product of a single (compound)
constant, C1, the difference between the polarizabilities of the
upper and lower states, and the reaction field (5). The latter is
proportional to the Lorenz–Lorentz
�������������������������������������������
solvent polarizability func-
tion, f1 = (n2 − 1)∙(n2 + 2), over the range 1.3 < n < 1.6, which
includes most common solvents. The derivation of this first term
in eq 1 from McRae's expressions is not obvious and is therefore
317
 Research: Science and Education

included in the online supplement. Term two results from the A 1.2

solute dipole–solvent induced-dipole interaction; term three 1.0

describes the solute dipole–solvent dipole interaction; term increasing

Absorbance
four represents the induced-dipole–induced-dipole (static dis- 0.8
pressure
persive) interaction. All four terms are preceded by minus signs
0.6
because all four types of interactions tend to lower the energy of
both the upper and lower electronic states of the solute. (Note, 0.4
however, that each term could make either a hypsochromic or a
bathochromic contribution to the overall solvatochromic shift, 0.2

depending on the relative magnitudes and signs of the polariz- 0.0

abilities and dipole moments of the solute in its ground and 400 500 600 700 800
excited states.) Wavelength / nm
Equation 1 may be used as follows. First, f2 = 0 for non-
polar solvents (D = n2) and only the first two terms in eq 1 B 1.2
survive. Thus plots of νu,l (solution) versus f1 for a given elec-
tronic transition of a given solute in several non-polar solvents 1.0 increasing
of different refractive index will be linear. Many examples appear pressure

Absorbance
0.8
in the literature (6) and a simple lab experiment based on a con-
venient solute chromophore can easily be established. Broaden- 0.6
ing of features in the solution spectra will make it impossible to
extract the exact values of νu,l (gas) from the intercepts of these 0.4

plots. However, the difference between the measured intercept 0.2

and the exact value of νu,l (gas)—obtainable, for example, from
supersonic jet spectra—will be small for absorbing solutes with 0.0
strong, well-resolved origin bands. 300 320 340 360 380 400

Extension of the Theory: Barochromism
Interesting features of the barochromism of the solute
follow by taking the derivative of eq 1 with respect to pressure.
Assuming that the polarizabilities and dipole moments of the
solute are independent of pressure at constant temperature,
d%Ou, l d% Ou, l solution
Wavelength / nm
Figure 1. (A) Visible (S1–S0) and (B) UV (S2–S0) spectra of azulene in
methylcyclohexane as a function of pressure (from ref 7). Apparent
absorbance increases with increasing pressure in the 0.1 to 600
MPa range are primarily due to increasing density of the solution.
The discontinuity in the S2–S0 spectra near 360 nm is due to a
change of excitation source in the spectrophotometer (from ref 7
with permission).


dP dP

 C1 B u  B l

df 1
dP Application to Azulene

 C2 Nu  Nl2 2 df 1

dP
(2) Many examples of the effects of applying high pressure
on the UV–vis absorption and emission spectra of solid and

 C3 Nl Nu  Nl

df 2
dP
 2 f2 C4 N l 2 B u  B l
ddfP
2
where df1∙dP = 6n∙(2n2 + 1)2dn∙dP ≥ 0 and df2∙dP = [3∙(D
+ 2)2](∂D∙∂P)n2 − [3∙(n2 + 2)2](∂n2/∂P)D, a quantity that may
be either positive or negative. Over a range of pressures from
0.1 MPa to several hundred MPa (1 bar to several thousand
bar) the wavenumber of a resolvable feature of an electronic
absorption system varies approximately linearly with P. Thus
values of dνu, l (solution)∙dP are obtainable directly from the
slopes of graphs of νu,l versus P. For non-polar solvents, f2 = 0,
and only the first two terms in eq 1 and eq 2 need be considered.
For sufficiently polar solvents, D >> n and df2∙dP ≈ ‒6n∙(n2
+ 2)2(∂n∙∂P)D < 0. Note that (i) df1∙dP is always positive in
solution, (ii) df2∙dP is negative when D >> n, and (iii) both
df1∙dP and df2∙dP are functions of only n when D >> n. These
expressions may be used to analyze the barochromism of solutes
in both polar and non-polar solvents.
solution-phase samples are available in the literature (8). Azu-
lene, often the subject of articles in this Journal (9–12), presents
an interesting example (7) and an excellent test of the theory
because its barochromism is known to be “anomalous”. That is,
the S1–S0 absorption system that gives rise to the blue color of
azulene exhibits an unusual (“anomalous”) hypsochromic (blue)
shift with increasing pressure (dνu,l ∙dP > 0), whereas the S2–S0
spectrum in the near-UV exhibits the usual bathochromic (red)
shift (Figure 1). All of the ground- and excited-state dipole
moment and polarizability data for azulene are available in
the literature and have been summarized in ref 7. The values of
dνu,l ∙dP are ‒0.236 cm‒1∙MPa for the electronic origin band of
azulene’s S2–S0 absorption system1 and +0.088 cm‒1∙MPa for
the origin of its S1–S0 absorption band. Thus the ratio of dν2,0/
dP to dν1,0∙dP is Robs = ‒2.7.
Suppose that solute dipole–solvent induced-dipole
interactions are largely responsible for the barochromism of
azulene in non-polar solvents. Then we should expect term
two in eq 2 to be dominant and a value of Robs ≈ Rd–id =
(μ2S2 − μ2S0)∙(μ2S1 − μ2S0). However, using the values of the

318 Journal of Chemical Education  •  Vol. 85  No. 2  February 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education 

ground- and excited-state dipole moments of azulene sum-
marized in ref 7, one calculates Rd–id = +1.3. On the other
hand, if dispersive interactions represented by term one in
eq 2 dominate, then we expect Robs ≈ Rpol = (αS2 − αS0)∙(αS1
− αS0). Using the best available literature values for azulene’s
ground- and excited-state polarizabilities results in a calcu-
lated value of Rpol = ‒2.6, closer to the observed value of Robs
= ‒2.7, and correctly predicts the "anomalous" hypsochromic
barochromism of the S1–S0 absorption bands. Thus, azulene’s
barochromism in non-polar methylcyclohexane is consistent
with the dominance of dispersive solute–solvent interactions
represented by the first term in eq 1 and in eq 2, with a smaller
contribution from dipole–induced-dipole interactions, term
two. Note that this is contrary to the usual explanation of
solvatochromism and barochromism in which the dominance
of dipolar interactions is assumed. In the case of azulene, the
unusual decrease in its polarizability on excitation to the S1
state is responsible for the “anomalous” blue barochromic shift
of the S1–S0 absorption band system. Solute dipole–solvent
induced-dipole interactions in non-polar solvents cannot
account for the observed barochromism since both μS1 and
μS2 are smaller in magnitude than μS0 (and are both opposite
in sign).
At constant pressure (near 1 bar), the blue shift in all
of azulene’s UV–vis absorption bands resulting from replac-
ing a non-polar solvent by a polar one is consistent with the
dominant influence of term three in eq 1. This term describes
an increase in both the S1–S0 and S2–S0 transition energies
in azulene since both excited-state dipole moments are op-
posite in sign (and smaller in magnitude) compared with the
ground-state. Term two in eq 1 makes a slightly smaller blue
shift contribution to the solvatochromism in polar acetonitrile
than in methylcyclohexane owing to its smaller refractive in-
dex, and term four makes no significant contribution since it
is proportional to f22∙r 6. Finally, the fact that the S1–S0 transi-
tion of azulene retains its anomalous barochromic behavior in
polar acetonitrile reflects the fact that dispersive interactions
dominate the pressure-induced frequency shifts, even in this
polar solvent. Students can easily look up values of n and D
and determine that df2∙dP is ca. 1.5 times larger in magnitude
than df1∙dP for acetonitrile. Thus term three in eq 2 represents
a red contribution to the barochromic shift that partially off-
sets the dominant (term 1) dispersion-induced blue shift for
the S1–S0 transition and that augments the dispersion-induced
red shift of the S2–S0 transition.
© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 2  February 2008  •  Journal of Chemical Education
Research: Science and Education
Final Remarks
The historical explanation offered for the solvatochromism
and barochromism of electrically neutral solutes in common
polar and non-polar solvents is that the spectroscopic shifts are
due primarily to differences in solute and solvent polarities. This
notion has been propagated in the chemical literature (6, 8) but
is clearly incomplete and actually is incorrect for “unusual” sol-
utes such as azulene. This topic presents an interesting example
of how reasonable, but incomplete or even incorrect, explana-
tions of common phenomena can survive for a long time in the
scientific literature.
Acknowledgments
This article arose from research supported initially by
the Natural Sciences and Engineering Research Council of
Canada and was pursued with the support of the University of
Saskatchewan.
Literature Cited
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5. McRae, E. G. J. Phys. Chem. 1957, 61, 562, with correction 1957,
61, 1687.
6. For a review see: Nicol, M. F. Appl. Spectrosc. Rev. 1974, 8, 183.
7. Okamoto, M.; Hirayama, S.; Steer, R. P. Can. J. Chem. 2007, 85,
432.
8. For a review see: Drickamer, H. G.; Frank, C. W. Ann. Rev. Phys.
Chem. 1972, 23, 39.
9. Castanho, M. A. R. B. J. Chem. Educ. 2002, 79, 1092.
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Derivation of the first term in eq 1
319