Physica D 137 (2000) 392–401

Far-infrared spectra of acetanilide revisited

A. Spire a,b , M. Barthes a,∗ , H. Kellouai a , G. De Nunzio a
a Groupe de Dynamique des Phases Condensées, cc26, Université Montpellier-2, 34095 Montpellier cedex 5, France
b Laboratoire de Physique Mathématique, Université Montpellier-2, 34095 Montpellier cedex 5, France

Received 9 April 1999; received in revised form 19 July 1999; accepted 20 July 1999
Communicated by A.C. Scott

Abstract
A new investigation of the temperature dependence of the far-infrared spectra of acetanilide and some isotopomers is
presented. Four absorption bands are considered at 31, 42, 64, and 80 cm−1 , and no significant change of their integrated
intensity is observed when reducing the temperature. The temperature induced frequency shift values and other properties of
these bands are consistent with an assignment as anharmonic lattice phonons. These results rule out the assignment of the 64,
80, and 106 cm−1 bands as normal modes of the polaronic excitation, as previously suggested. ©2000 Elsevier Science B.V.
All rights reserved.
Keywords: Polaron; Localized modes; Nonlinear excitations; Dynamics; Far-infrared spectra

1. Introduction roughly constant. (ii) It appears in both infrared and

The possibility of finding experimental manifesta-
tions of nonlinear coherent structures like breathers or
solitons, at a microscopic scale in solid state physics,
is an exciting goal in order to check recent theories
and to get a better understanding of the properties of
matter. In this field, the problem of the anomalous
peak at 1650 cm−1 in the Amide-1 spectrum of ac-
etanilide (C6 H5 NHCOCH3 , or ACN) [1], and some
of its deuterated derivatives [2,28], has attracted many
experimental and theoretical studies in recent years.
This “unconventional” infrared peak has the fol-
lowing properties: (i) Its intensity is strongly temper-
ature dependent, in contrast to absorption bands from
quasi-harmonic vibrational modes whose intensity is
∗Corresponding author.
E-mail address: mariette@gdpc.univ-montp2.fr (M. Barthes).
Raman spectra at the same frequency, but only from
crystalline and not from amorphous ACN.
Possible explanations for this unconventional in-
frared and Raman band have been much debated The
first proposed theoretical model was a self-trapped
localized state created through coupling of Amide-1
quanta with optical phonons and sometimes labeled
as a “Davydov soliton” [3] or a “vibrational polaron”
[4–6]. This nonlinear excitation — if it exists — should
be able to translate along the lattice without energy
dissipation, and may be involved in some biological
processes involving energy transfer (cf. ATP depen-
dent reactions, muscle contraction, DNA replication,
gene activation ?), see e.g. [7] or [29].
Other hypotheses have been also suggested and dis-
cussed in order to explain this unconventional band,
for example Fermi resonance [8], or alternatively the
presence of either static conformational substates,

0167-2789/00/$ – see front matter ©2000 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 2 7 8 9 ( 9 9 ) 0 0 1 7 8 - 5
 A. Spire et al. / Physica D 137 (2000) 392–401
or of a dynamical exchange of the amide proton
in a double well potential along the N–H...O bond
[9].
Related spectral anomalies have been also discov-
ered in other organic systems with intermolecular
H-bond networks [10], including some amino-acids
and poly-alanines [11].
At the present time, among the available theories,
the polaron model gives the best agreement between
properties and predictions [1,2,12,13,28].
Moreover, a strong temperature dependence of the
intensity of three absorption bands in the far-infrared
spectrum at 120, 80, and 64 cm−1 [14] has been re-
ported. Changes of intensity of about 90% were re-
ported in the range 10–300 K, analogous to that of
the unconventional Amide-I mode, and it was sug-
gested that this temperature dependence was a confir-
mation and a new experimental signature of solitons
(“polarons”).
Recently, Kalosakas, Tsironis and Aubry (KTA)
[15,30] succeeded in calculating the normal modes
of the self-trapped state, using theories connecting
the polaron problem to breathers, suggesting new
and experimentally testable predictions for the po-
laron eigen-frequencies that could be found in the
far-infrared region. They also suggested the exis-
tence of a polaron glass at low temperature, with
long-lived and perhaps experimentally observable
localized modes. This distribution of defects should
keep the system out of equilibrium for reasonably
long timescales and may be responsible for far-IR
absorption.
However, no other experimental proof of the exis-
tence of polarons has been demonstrated: no broaden-
ing in the quasielastic neutron scattering spectra has
been observed [16], as it may be expected from some
dynamic disorder created by such localized defects.
So it became necessary to consider in more detail the
properties, and specifically the localized nature of the
far-infrared spectra in ACN and in some related com-
pounds.
In this paper, we present a new study of the
far-infrared spectra of ACN (single crystal and micro-
crystalline powder) and three of its deuterated deriva-
tives (microcrystalline powder of: C6 H5 NHCOCD3 ,
393
or D3-ACN; C6 D5 NHCOCH3 , or D5-ACN;
C6 D5 NHCOCD3 , or D8-ACN), in a temperature
range of 5–300 K.
These new data are compared to other measure-
ments of the low frequency dynamics in ACN and
derivatives obtained by Raman [17–19,31], neutron
scattering [16,20], and data from computer modeling
[21]. Finally, the validity of attempts to connect the
calculated eigen-frequencies of the polarons to the ex-
perimental spectral lines of ACN is analyzed and ques-
tioned.
2. Experimental
Experiments were carried on a Bruker IFS 113V
spectrometer, with a resolution of 0.5 cm−1 , and then
of 0.2 cm−1 . Two liquid He cooled Si bolometers
were used in the range 20–50 cm−1 and 17–100 cm−1 ,
with a 20 mm mylar beamsplitter. A DTGS pyroelec-
tric detector was used to collect data in the range
50–200 cm−1 . At each temperature before collecting
the intensity (I ) transmitted by the sample, the spec-
trum of the incident light (I0 ) is also recorded, to
avoid changes of absorbance of the windows of the
cryostat when varying the temperature.
Energy, halfwidths and line shapes of the absorp-
tion peaks were determined using a nonlinear least
square analysis program. The thickness of the differ-
ent samples were around 0.1–1 mm and their trans-
parency was sufficient to collect the transmitted inten-
sity. Single crystals were platelets oriented in the b,c
plane (the hydrogen-bonded chains are parallel to the
b direction).
3. Infrared spectra
In Fig. 1 the absorbance of a single crystal of ACN
is shown at several temperatures. Three bands at 42,
65 and 80.5 cm−1 (at ∼ 5 K) are observed. Another
absorption bands also exists at ∼ 31.3 cm−1 , but is not
observed in the spectrum of the single crystal. This
band may be drowned in the periodic oscillations of the
background resulting from the interferences between
394 A. Spire et al. / Physica D 137 (2000) 392–401

Fig. 1. FIR absorbance of a single crystal of ACN at different temperatures: (—) 5 K; (. . . . . . ) 70 K; (− · − · −) 108 K; (-----) 164 K.

Fig. 2. Absorption spectra at 31.3 and 42 cm−1 (at 5 K) in crystalline powder of ACN: (—) 50 K; (. . . . . . ) 100 K; (− · − · −) 200 K; (-----)
250 K.
 A. Spire et al. / Physica D 137 (2000) 392–401 395

Fig. 3. (A) Absorption spectra in crystalline powder of D3-ACN: (—) 5 K; (. . . . . . ) 70 K; (− · − · −) 90 K; (-----) 136 K; (– – –) 228 K.
Insert: FlR bands in D5-ACN: (—) 100 K; (. . . . . . ) 50 K; (– – –) 5 K. (B) Absorption bands in D8-ACN: (—) 5 K; (. . . . . . ) 70 K; (− · − · −)
108 K; (-----) 164 K; (– – –) 290 K.

multiple reflections of the light by the surfaces of the low it to be active if this band is of B3u symmetry.
crystal. More likely, the experimental polarization ge- This last band appears more clearly in the spectrum of
ometry (the electric field of the incident light being a powder sample (Fig. 2). Following the same argu-
parallel to the b,c plane of the crystal) does not al- ment, the weak intensity of the band at ∼ 80 cm−1 in
396 A. Spire et al. / Physica D 137 (2000) 392–401

Fig. 4. Absorption spectra in crystalline powder of ACN (resolution 0.2 cm−1 ): (-----) experimental spectra; (—) result of the fit; (− · − · −)
and (-..-..-) Lorentzians; (. . . . . . ) tail of the band at 106 cm−1 taken as a Lorentzian: (A) T = 55 K; (B) T = 88 K; (C) T = 150 K; (D)
T = 180 K.

the spectra of the single crystal may also be explained
by its forbidden symmetry.
All these bands have been observed in the spec-
trum of the three deuterated derivatives, with compa-
rable energy and intensity when varying the temper-
ature (Fig. 3). The band at ∼ 31 cm−1 and the band
at 42 cm−1 consist of only one component, which can
be fitted by one Gaussian.
The precise measurement of the temperature depen-
dence of the intensity of these peaks (which is the
 A. Spire et al. / Physica D 137 (2000) 392–401 397

Fig. 4. (Continued).

main purpose of the present study) is not straight-
forward. In some cases, an apparent change of about
50% of the integrated intensity is observed over the
full range of temperature. However, the bands at 65
and 80 cm−1 share some intensity with each other and
with the wide band at ∼ 106 cm−1 when the temper-
ature increases above 60 K, so a proper subtraction of
the background has to be carried out. Secondly, and
this effect is especially strong for single crystals, the
periodic oscillations resulting from interferences have
also to be subtracted. Moreover, the background itself
increases with increasing temperature, in connection
398 A. Spire et al. / Physica D 137 (2000) 392–401

Fig. 6. Temperature dependence of the width of the FIR bands.

Fig. 5. Integrated intensity of the bands at 80 cm−1 (dark squares),
80 cm−1 (dark circles), 64 cm−1 (open circles), 42 cm−1 (crosses)
64 cm−1 (open circles), and 42 cm−1 (triangles).
and 31 cm−1 (dark squares).

with some incoherent scattering of light, related to the frequency of the band) ranged from 5.3 × 10−4 to
thermal motion of some atoms. (Such an effect is also 6.8 × 10−4 cm−1 K−1 . They are consistent with ex-
observed in some biomolecules, like lysozyme [22], pected values for external modes, and in good agree-
and disappears at LHeT.) ment with previously measured values from Raman
To minimize these effects, new spectra with an im- scattering [18].
proved resolution (0.2 cm−1 ) have been collected, with The symmetry of these vibrations may be esti-
a very thin powder sample. The spectra are fitted with mated with the help of the calculations developed
Lorentzians, and for temperatures above 60 K the con- by Hayward et al. [21]. The assignment is given in
tribution of the tail of the peak at 106 cm−1 is taken Table 1 .
into account. The experimental spectra, the individual Several spectra collected between 100 and
components and the result of the fit are given at several 200 cm−1 are shown in Fig. 8. The temperature
temperatures in Fig. 4. The integrated intensity of the dependence has been studied for every sample. The
bands deduced from this careful analysis of the new width of each absorption band increases with increas-
set of data (Fig. 5) is, within the experimental accu- ing temperature. However no spectacular change of
racy, approximately constant. This is in contradiction
with the previous measurement (Fig. 2 in [14]).
All four bands experience a limited increase of
width (Fig. 6) when increasing the temperature.
This behavior is similar to that of the low-frequency
Raman bands [19], the width being roughly linearly
dependent on temperature.
The energy of the four bands increases quasi-linearly
with decreasing temperature (Fig. 7) and becomes
constant at around 30 K. The temperature in-
duced frequency shift values, 1ν/1T , vary from
−0.022 cm−1 K−1 for the 31 and 42 cm−1 band to
−0.038 and −0.048 for the 64 and the 80 cm−1 bands,
respectively. The fractional frequency shift values
(obtained by dividing 1ν/1T by the low temperature Fig. 7. Temperature dependence of the frequency of the FIR bands.
 A. Spire et al. / Physica D 137 (2000) 392–401 399

Table 1
Frequency (5 K) experimental (cm−1 ) Frequency Assignment Symmetry character of
calculated [20] the crystal mode [20]
ACN ACN D3- D5- D8-
crystalline powder

– 31.3 31.2 31.3 31 25 Translation B3u

41.5 41.5 41.2 41.5 41 42 Translation B1u
63.5 (Weak) 63.4 63 Librational B3u
64.4 64.4 61.5 60.8 55 Librational B1u
65 65 63.4 62a 62.2 66 Librational B2u
80 80 78.5 80a 77.4 79 ␶ Phenyl B3u
81 81 79.5 79 79 Translation B2u
(Weak) (Weak) 83 83 Librational B1u
a From Ref. [28].

the integrated intensity could be detected. No strong
temperature dependent band at 118 or 128 cm−1
appeared, as reported in [14].
The band at 102 cm−1 , observed on D3-ACN and
D8-ACN is certainly one component of the CD3 tor-
sional mode. In the same way, the band observed
at 150 cm−1 , only in ACN, D5-ACN, and ACN-ND
(or C6 H5 NDCOCH3 ), is related to the CH3 torsion.
The intense band at 107 cm−1 (at 15 K) in ACN ex-
hibits a large energy shift with temperature (92 cm−1
at 290 K), so it may be assigned to the H-bond strain.
Its height decreases strongly with increasing temper-
ature, with a simultaneous increase of its width, so it
is not possible to prove a significant variation of its
integrated intensity.

4. Discussion

Our new investigation of the FIR spectra of ACN

Fig. 8. Spectra of five isotopomers in the range 100–200 cm−1 .
and derivatives has failed to confirm the assertion of
[14] of anomalous behavior of these low frequency
modes. The careful analysis of the FIR bands does
not reveal any significant change of the intensities
with decreasing temperature, within the experimental
accuracy.
The temperature dependence of the energy of the
modes below 100 cm−1 is consistent with the expecta-
tions for external modes, and the frequency shift val-
ues are comparable to those obtained in Raman scat-
tering. The linear increase of the widths of the bands
with increasing temperature reflects a “classical” an-
harmonicity [23], already observed for different Ra-
man bands in the same range of frequency, on ACN
and its derivatives [15–17,30,31].
400 A. Spire et al. / Physica D 137 (2000) 392–401
Moreover, the observed frequencies and the symme-
try of the four bands below 100 cm−1 are in reasonable
agreement with molecular dynamics simulations [21],
so their assignments as lattice phonons seem estab-
lished. On the other hand, most of their characteristics
are inconsistent with assignments as eigen-frequencies
of the polaron. First, the temperature dependence of
this part of the vibrational spectrum, already studied
by inelastic neutron scattering with different instru-
ments (1N6 at ILL [18], FDS at LANSCE [19], TFXA
at ISIS [23]) has not revealed any significant anomaly
of intensity, in agreement with our FIR data. Secondly,
in the present work, the bands at 64 and 80 cm−1 are
observed as well in pure ACN showing an “anoma-
lous Amide-1 mode”, as in D3-and D8-ACN which
have no anomaly in the Amide-l range. The Raman
scattering studies [17–19,31] report no anomaly in the
low frequency spectra, either. All these effects favor
the attribution given in Table 1, and disprove the in-
terpretation suggested in [14].
Interestingly, the width of the band related to the
deformation of the hydrogen-bond, at 107 cm−1 , does
not follow a power law with T [2,28], as expected
in different theories of anharmonicity [24], but obeys
an exponential law. The width of the “anomalous”
mode at 1650 cm−1 , and of the γ (NH) mode at
770 cm−1 , have also an exponential dependence with
T . Other infrared, (at 1497 cm−1 [2,28]) and Raman
(at 1503 cm−1 [19]) bands in ACN have been found
to obey the same law (their widths are shown for com-
parison in Fig. 9). These last two bands also show an
anomalous increase of intensity at low temperature,
and they were tentatively assigned to the overtone of
the out-of-plane bending of the amide proton. So it
appears that the “mechanic” or “optic” nonlinearities
of the hydrogen bond motions may be very different
from that of the other vibrations of the solid. Is this
specific anharmonicity at the origin of the whole set
of spectroscopic anomalies?
5. Conclusion
We have reexamined the far-infrared spectra of
ACN and of three isotopomers. Below 100 cm−1 four
Fig. 9. Temperature dependence of the width of the mode at
107 cm−1 (+++) (presumably the H-bond strain), as compared
to the width of the IR band at 770 cm−1 (× × ×) (out-of-plane
N–H bond), of the IR band at 1503 cm−1 (circles) (overtone of
γ N–H), of the Raman band at 1497 cm−1 (diamonds), and of the
Raman anomalaus mode at 1650 cm−1 (triangles).
absorption bands have been observed that exhibit
some usual anharmonic behavior when decreasing
the temperature: energy increase and narrowing of
the half-width of the peak. However, the integrated
intensity of these peaks remained constant, within the
experimental accuracy, in the full range of tempera-
ture. So, we assigned these peaks to lattice phonons,
in agreement with data from molecular dynamics
simulations.
Though this new investigation does not confirm the
evidence for the normal modes of vibrational polarons,
and there is no direct proof whether vibrational po-
larons or other nonlinear coherent structures do exist
in this material, some properties of the ACN spectra
doubtlessly result from nonlinearities.
Previous experiments have demonstrated the part
played by the coupling of different oscillators:
1. The large number of overtones of the “anomalous”
band at 1650 cm−1 [19,25], is a signature of a “lo-
calized” mode, that is an oscillator “dressed” by
the lattice phonons [5,26]. The part of the lattice
phonons is confirmed by the fact that the mode at
1650 cm−1 is found only in crystalline ACN, and
not in amorphous ACN [1]. Moreover, this effect
 A. Spire et al. / Physica D 137 (2000) 392–401
together with the lack of the mode at 1650 cm−1
in the D3-and D8-derivatives [2,28] are not ex-
plained under the assumption of a Fermi reso-
nance which appears unlikely.
2. The fine structure of vibrational sidebands ob-
served around the stretching mode of the amide
proton (or ν(N–H) vibration) is a general prop-
erty in systems in which networks of hydrogen
bonds are created [27,32]. This width and fine
structure are partly explained by the large anhar-
monicity and the strong coupling of the ν(N–H)
stretch with the ν(N–H)...O (also called hydrogen
bond strain), and other intermolecular deforma-
tions of the chain. However, as yet no theoreti-
cal model [4,25], is able to properly take into ac-
count the temperature dependence of this part of
the spectrum [2,28] . This is still an open ques-
tion, indicating complex nonlinear interactions in
molecular crystals.
3. The specific anharmonicity revealed by the ex-
ponential temperature dependence of the widths
of the absorption bands related to amide vibra-
tions also reflects the importance of nonlinear in-
terplay between the hydrogen bond and other os-
cillators. This should be accounted for in future
theories.
Acknowledgements
We thank G. Tsironis, S. Aubry and G. Kalosakas
for useful discussions. This work is a part of the
“PluriFormations” Contract “Dynamique Nonlinéaire
et Chaines Moléculaires” Université Montpellier
II–CNRS–MENRT.
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