Surface Science 134 (1983) 675-688 675

North-Holland Publishing Company

A SURFACE-ENHANCED RAMAN SCATTERING STUDY OF CTAB

ADSORPTION ON COPPER

A.L. DENDRAMIS, E.W. SCHWINN and R.P. SPERLINE

Miami Valley Laboratories, The Procter and Gamble Co., Cincinnati, Ohio 45247, USA

Received 29 April 1983; accepted for publication 22 August 1983

Surface-enhanced Raman spectroscopy (SERS) has been used to study, in situ, the adsorption
of cetyltrimethylammonium bromide (CTAB) on copper. The data obtained allow the determina-
tion of CTAB’s adsorption rate from aqueous solution and are consistent with physisorption or
weak chemisorption via the quatemary ammonium group. The use of “surface selection rules” to
derive orientation information is examined.

1. Introduction

Surfactant adsorption on metal surfaces is extremely important in a variety

of fields such as adhesion, lubrication, detergency and corrosion inhibition.
Consequently, there is considerable interest in determining the structure of the
adsorbed species on the metal surface as well as the dynamics of the adsorp-
tion. The majority of the presently existing techniques can provide either the
first type of information or the second, but not both. In addition, the
techniques that are most useful for providing structural information more
often. than not require prior separation of the metal surface from the medium
containing the active species. This step, for obvious reasons, may alter the very
surface characteristics one is interested in studying. Therefore, there is a strong
need for a technique that can interrogate the metal surface in situ, and at the
same time provide structural as well as dynamic information on the surfactant
being adsorbed. A technique that appears to be promising in this respect is
SERS. Although, judging from the current understanding of the technique’s
underlying principles [l], its use may be limited to just a few metals, it
nevertheless has great potential for providing answers to some basic questions
regarding surfactant adsorption on metal surfaces. Such questions are related
to the identification of the actual species adsorbed, its orientation, its rate of
adsorption/desorption, and perhaps quantitation, all under in situ conditions.
SERS was initially observed in 1974 [2], but its potential was not recognized
until 1976 [3] and its popularization as a powerful analytical technique did not
materialize until very recently [4]. The technique is based on the fact that the

0039-6028/83/0000-0000/$03.00 0 1983 North-Holland

616 A. L. Dendramis et al. / SERS study of CTAB on copper

Raman scattering signal of a species in contact with, or in close proximity to, a

metal surface is enhanced by several orders of magnitude over that of normal
Raman. This enhancement provides to Raman spectroscopy which is, inher-
ently, a highly selective structural technique, the sensitivity required for surface
studies. The ability to gather dynamic information is also secured by recent
advances in the area of multichannel detection [5]. In addition, because SERS
is a scattering process and involves a highly directional light source (laser), it
affords unparalled in situ capability, thus meeting the third criterion for being
a good interfacial tool. The ease of focusing a laser beam provides the added
benefit of good spatial resolution, if needed.
So far, SERS studies of long-chain surfactant molecules have been rather
sparse and concentrated on silver or gold surfaces, with no dynamic informa-
tion content [6-lo]. The purpose of this paper is to expand on the usefulness
of SERS for studying in situ the adsorption characteristics of long hydro-
carbon-chain cationics on copper. Information on CTAB, a well-known repre-
sentative of this class of surfactants, will be presented and we hope that this
will provide some stimulus for further research in this important area of
surface science. Although CTAB vibrational data in solution and as a pure
solid have been reported previously [ll-131, to our knowledge there is no such
information available for CTAB in its adsorbed state on any type of surface.

2. Experimental

Cetyltrimethylammonium bromide (Fisher Scientific, reagent grade) was

purified by recrystallization from acetone and its purity verified by TLC. The
copper surface employed was the tip of a rod, 3.18 mm in diameter (Alfa
Products, 99.999% purity). It was polished with 0.05 pm alumina suspension or
1 pm diamond polishing paste (Buehler Ltd.) and rinsed with the same highly
purified water used for preparing the surfactant solutions. The water was
singly distilled and passed through a Milli-Q@ purification apparatus (Milli-
pore Corp.). The rod was kept immersed in the CTAB aqueous solution
throughout the experiment. The polished surface was positioned so that the
normal to the surface was at a 60’ angle with respect to the impinging laser
beam. The solutions were purged with nitrogen gas before and during the
experiment and air was excluded from the cell headspace by a flow of nitrogen
gas above the solution. However, the omission of such precautions did not
seem to affect the data in any significant way.
Raman spectra were recorded with a Spex Ramalog 5 spectrometer inter-
faced to an 8-bit Intel microcomputer system. The gratings were holographic,
1800 grooves/mm, and the thermoelectrically cooled photomultiplier tube, an
RCA C31034. The signal was processed by standard photon counting tech-
niques. Excitation radiation was provided by a Coherent model 490 DCM dye
 A.L. Dendramis et al. / SERS study of CTAB on copper 617

laser that was pumped by a Coherent Innova 90-3 argon-ion laser. The power
at the sample was 40 to 100 mW and the excitation wavelength was 661 nm.
The spectral resolution was approximately 4 cm-‘. A Claassen filter was used
to reject spurious lines from the dye laser. Spectral frequencies are reported to
f2 cm-‘.
For the voltage dependence studies the copper rod served as the working
electrode. Inserted in the cell were also a saturated calomel reference electrode
and a platinum auxiliary electrode. An EG&G/PARC model 174A polaro-
graphic analyzer was the voltage source.
The spectra of pure solid and concentrated aqueous CTAB solution were
obtained from samples contained in glass capillary tubes.

3. Results and discussion

Figs. la and 2a show parts of the Raman spectrum of CTAB adsorbed on

copper. The adsorption took place by bringing in contact a mechanically
polished copper rod with a 1 x 10p4M CTAB solution in water. For compari-
son purposes the normal Raman spectra of a O.lM CTAB aqueous solution
and pure solid CTAB are included in figures lb, 2b and lc, 2c, respectively.
The band positions and corresponding tentative assignments are listed in table
1. The assignments are based on extensive comparisons with vibrational
spectra of other long-chain molecules bearing the -N+(CH,)3 headgroup
[14-201. Our spectra of CTAB in solution and as a pure solid are in excellent
agreement with those reported by Kalyanasundaram and Thomas [ll]. How-
ever, some of our assignments differ from theirs, reflecting the benefit derived
from the extensive amount of vibrational literature published on similar
molecules since their paper appeared.

3. I. Spectrum origin

The strong similarity of the surface spectrum to that of CTAB in solution

rules out the possibility of any major chemical modification of CTAB upon
adsorption. The low solution concentration also eliminates any contribution to
the surface signal intensity from CTAB molecules in solution. This was verified
by the complete absence of Raman signal from a 1 X 10d4M CTAB solution.
The spectrum was taken in a double pass cell to account for the presence of a
reflecting surface in the SERS sampling configuration. Based on these consid-
erations it is then reasonable to assume that the observed spectrum originates
from CTAB molecules adsorbed on the copper surface. The possibility that
there are enough CTAB molecules on the surface to yield a normal Raman
spectrum is eliminated by the fact that no spectrum is observed when laser
excitation wavelengths of 514.5 and 488.0 nm are employed. It is also highly
678 A.L. Dendramis et al. / SERS study of CTAB on copper

1700 1500 1300 1100 900 700 500 300

4 A7 (cm-‘)

Fig. 1. The mid-frequency region in the Raman spectra of CTAB: (a) adsorbed on copper, (b)
O.lM aqueous solution, and (c) pure solid.

unlikely that the intense surface signal is due to resonance Raman scattering
from a Cu-CTAB complex. If this were the case one would expect more
pronounced differences between the surface and solution spectra with regard
to band frequency positions. Our inability to form a complex yielding a
resonance Raman spectrum by mixing in solution CTAB and monovalent or
divalent copper halides in various stoichiometries lends further support to this
contention. It is, therefore, safe to conclude that the observed spectrum is
indeed a surface-enhanced spectrum.
 679

0 3050 3000 2950 2900 2950 2000 :

a nJ(cm-I)
Fig. 2. The C-H stretching region in the Raman spectra of CTAB: (a) adsorbed on copper, (b)
O.lM aqueous solution, and (c) pure solid.

________
_____
4.

’
3-
I

SERS /-
I Cti
2-

I-

IO 20 30 40 60 60 70 00 90 1214

t (mid -
Fig. 3. Relative intensity of SERS for CTAB (integrated C-H stretching range) as a function of
contact time between copper and CTAB solution (10e4M).
680 A.L. Dendramis et al. / SERS study of CTAB on Cooper

Table 1
Raman frequencies of cetyltrimethylammonium bromide adsorbed on copper, in O.lM aqueous
solution and as a pure solid; sh denotes a shoulder; the values in parentheses are the corresponding
depolarization ratios

CTAB frequencies (cm-‘) Tentative

assignment
SERS O.lM solution Solid

371 354 C4Nt deformation

392 384
404 404
424 (sh) 419 415
449
455 455 454 C,N+ deformation
480
493 491 494
504
523 522
542 536
599 595
624 625 cu,o
687
732 730 CH 2 rock?
754
763 (0.67) 760 ( i 0.1) 763 CN + stretch
774
801 802
836 839 832 CH, deformation
873 868 864
891 886
904 912 909 CH, rock,
944 (sh) 939 CN+ stretch
964 970 963 t
986
1004 1013
1029 1044
1062 (sh) 1064 1063 C-C stretch
1086 1084 1102
1124 (sh) 1122 1127
1144 1140
1159 1152
1169
1196 1184
1214 1214 CH 2 wag
1232 1231
1252 1248
1272 1274
1306 1302 1295 CH, twist
1313
1344 1350 1359 CH r wag,
1374 1370 1369 CH, deformation
1393 (sh) 1400 1397
 A.L. Dendramis et al. / SERS study of CTAB on copper 681

Table 1 (continued)

CTAB frequencies (cm-‘) Tentative

assignment
SERS O.lM solution Solid

1416
1449 (0.72) 1450 ( < 0.1) 1442 1 CH 2 scissors,
1464 CH, deformation
1484 1480 1481
1538
1576
1602 1599
2844 2854 2850 CH, sym. stretch
2873
2884 2890 2883 1 CH, as. stretch
2908 2900
2932 2935 2945 1 Term. CH, sym. stretch,
2961 2961 Term. CH, as. stretch,
2973 2974 2974 Headgroup CH, sym. stretch
2987 3009
3022 3020
3029 Headgroup CH, as. stretch
3029 3042 3034

3.2. Adsorption rate

CTAB appears to have a strong affinity for copper. Fig. 3 shows a plot of
the integrated SERS band intensity for the CH-stretching region, I~~Rs, as a
function of time the copper surface remains in contact with a 1 x 10p4M
aqueous solution of CTAB. ICH SERS is taken as a measure of the amount of
adsorbed surfactant. Adsorption is rather fast but still slod enough to be
followed by PMT detection. Although not evident from the graph, CTAB’s
packing/orientation does not change with increasing surface coverage. This
follows from the constancy of the relative SERS band intensities throughout
the adsorption process. CTAB’s rate of adsorption increases with increasing
solution concentration. However, the ultimate amount of surfactant adsorbed
and its packing/orientation remain the same as evidenced by the invariability
of the SERS spectrum with changing CTAB solution concentration. The
concentration range studied was from 1 X 10e4 to 5 X 10p3M, encompassing
CTAB’s critical micelle concentration (CMC) which is known to be 9 x 10p4M
[21]. The onset of micellization does not appear to cause any discontinuity in
the change of adsorption rate as a function of surfactant solution concentra-
tion.
The usefulness of SERS as an accurate means of determining a surfactant’s
adsorption rate rests on the assumption that the surface roughness does not
change in the course of the experiment or, at least, does not change in a way
affecting the dynamic information collected. The expected specific adsorption
682 A.L. Dendramis et al. / SERS study of CTAB on copper

of bromide ions on copper and the known photosensitivity of copper halides

coupled with the presence of the laser beam in our experiment may be
sufficient to invalidate such an assumption. Because of these concerns, SERS
experiments were performed with copper surfaces which had been exposed to
potassium bromide solutions, with or without laser illumination, prior to their
contact with the CTAB solution for adsorption rate studies. No significant
differences could be detected in the overall adsorption kinetics. It appears
unlikely that surface roughness changes occurring over the course of the
experiment contributed to the observed rates. The seemingly slow adsorption
rate of CTAB shown in fig. 3 may have resulted from low CTAB concentration
in the aqueous solution (1 x 10W4M). For instance, at one order of magnitude
higher concentration (1 X 10e3M), the adsorption rate was found to increase
by a comparable amount. To verify this notion, an independent determination
of the adsorption rate was made using surface tension as a measure of
surfactant depletion due to adsorption. For this experiment, a 1 X 10P4M
CTAB aqueous solution was brought into contact with a high surface area
copper powder. The results were similar; equilibrium was attained in tens of
minutes rather than in’ seconds.

3.3. Spectral analysis

Despite the similarity between the SERS spectrum and that obtained from
solution, there do exist some striking differences between the two spectra.
These are the unusually large intensity enhancement of the 1449 cm-’ (CH,,
CH, bending) and 763 cm-’ (C-N+ stretch) bands, the almost complete
disappearance of the 1306 cm-’ (CH, twist) band and the predominant
character of the 2844 cm-’ band within the high-frequency multiplet
(CH-stretching region). Other major differences, which are not however perti-
nent to the main topic in this paper, include the large contributions of water in
the solution spectrum (1635 cm-’ band) and of a species containing a Cu-0
bond in the SERS spectrum (624 cm-’ band). The latter assignment is
supported by the intensity enhancement of this band when N, is not bubbled
through the solution. In addition, it is present regardless of CTA’s counterion
(Cl- or Br-) and its frequency position matches that of a band observed in the
Raman spectrum of Cu,O [22].
As has been the case with the majority of the SERS spectra published to
date, spectral analysis remains a formidable challenge because of the lack of
firmly established selection rules [23]. It is a difficult problem to solve because
of the complexity of the surfaces involved and the possible synergistic effect of
a variety of enhancement mechanisms which have been well documented in the
literature [24]. Nevertheless, it is still worthwhile to discuss the data and what
they mean regarding the mode of adsorption and orientation of the adsorbate.
At first glance, the overall pattern of the CH-stretching region, which is
 A.L. Dendramis et al. / SERS study ofCTAB on copper 683

dominated by the 2844 cm-’ band, implies a disordered long chain [25,26]. It
is not clear, however, that the same assignments as those made for the normal
Raman spectra of such molecules are valid for their SERS spectra. Evidence
that this may not be the case comes from SERS spectra of compounds with a
similar headgroup but without the long chain, such as tetramethylammonium
iodide and trimethylphenylammonium bromide [27]. Although their overall
CH-stretching frequency patterns are different from each other and from that
of CTAB, they too exhibit strong bands around 2850 cm-’ and in fact also
contain a broad structure between 2850 and 2950 cm-‘, as found for CTAB. It
is possible, then, that methyl groups from the surfactant headgroup are largely
responsible for the intensities of these bands which are normally assigned to
long-chain methylene asymmetric and symmetric stretching motions. This truly
upsets the entire scheme on which decisions are often based regarding the
conformational and packing characteristics of molecules having long hydro-
carbon chains. It also affects our ability to use the vast literature data on such
molecules for understanding CTAB’s structure in its adsorbed state.
The simplified mid-frequency spectrum, however, may be an alternative
source of the information we are seeking. Two key features in this frequency
range stand out and actually shape, in our opinion, the approach to be
followed for a consistent interpretation throughout the SERS spectrum. First is
the anomalously high intensity of the band at 763 cm-’ assigned to a C-N+
stretch. Second is the almost complete disappearance of the band at 1306 cm-’
assigned to the CH, twisting motion. It should be noted that the latter band is,
actually, the only one of moderate to strong intensity in the mid-frequency
range which can be unequivocally assigned to a CH, motion. All the other
bands which are candidates for CH,-vibration assignments are in ranges that
overlap those of CH, vibrations. These two facts combined tempt one to think
of the possibility that the headgroup vibrations are preferentially enhanced
over those of the long chain. We will then proceed to see whether the rest of
the spectrum is consistent with this notion. Certainly, the earlier discussion
regarding the CH-stretching region appears to be compatible with this concept.
The strong band at 1449 cm-’ is in an area where CH, bending and CH,
bending motions both contribute. In a long-chain molecule without the
(CH,)3N+ group this band would be automatically assigned to CH, scissors.
However, molecules containing the (CHJ),N+ group exhibit strong bands in
this area due to CH, deformations. This is evident from normal Raman as well
as SERS spectra of tetramethylammonium iodide and trimethylphenylam-
monium bromide [18, 27, 281. Therefore, it is not unreasonable to assign the
1449 cm-’ band primarily to deformation of methyl groups attached to the
quatemary nitrogen. Definitive proof of this can only come of course from
obtaining spectra of selectively deuterated CTAB which was not available to us
when this work was done. Other relatively dominant features in the spectrum
include the low frequency bands at 371, 455, and 542 cm-’ and those at 904,
684 A. L. Dendramis et al. / SERS study of CTAB on copper

964, and 1144 cm-‘. The first two could be easily assigned to C,N+ deforma-
tions based on literature reports on similar molecules [29]. The 542 cm-’ band
is at least partly due to a species containing a Cu-0 bond since its behavior
appears to closely resemble the 620 cm-’ band’s behavior, noted earlier. The
904 and 964 cm-’ bands probably have their origin in methyl rocking
vibrations from the (CH,),N+ group and may be mixed with C-N’ stretching
modes [30]. Finally, the band at 1144 cm-’ is best assignable to a skeletal
mode of the long chain, although it may be due to a combination mode
stemming from bands associated with the headgroup.
From the above discussion, then, it is obvious that the main features of the
SERS spectrum may be reasonably accounted for by invoking preferential
enhancement of the vibrational bands associated with the (CH,)3N+ group.

3.4. Adsorbate orientation

Ever since the discovery of the SERS effect it has been theorized that bands
corresponding to vibrations of adsorbed molecules that give rise to polarizabil-
ity changes perpendicular to the metal surface will be preferentially enhanced
in SERS [31]. In fact, some experimental evidence has been presented to
support this concept [32]. Therefore, it is interesting to see what the implication
of such a “surface selection rule” is with regard to CTAB’s orientation on the
copper surface. Based on our spectral data and on elementary considerations
regarding the direction of oscillating induced dipole moments for the various
CTAB normal modes, the following CTAB orientation is suggested. The chain
has most C-C bonds nearly parallel to the surface, while the headgroup is in
close proximity to the surface with the three methyl groups positioned symmet-
rically over it.
Placing the C-C bonds parallel to the surface would explain the absence of
any strong bands due to C-C stretching vibrations since the oscillating
induced dipole moment vectors associated with such modes would be parallel
or nearly parallel to the plane of the metal surface. Such an arrangement of
C-C bonds is, in addition, compatible with weak bands for the CH, twisting
(1306 cm-‘) and CH, scissoring (- 1450 cm-‘) motions. It would also call for
a weak CH, symmetric stretch and a strong CH, asymmetric stretch. This, too,
is not inconsistent with the observed spectrum, since the high intensity of the
band whose frequency is normally considered representative of a symmetric
CH, stretch (- 2850 cm-‘) may be largely due to the N+-attached methyl
groups, as discussed previously.
Many of the theoretical models for SERS predict stronger enhancement for
bands associated with molecules that are closer to the surface [24]. Experimen-
tal evidence, so far, supports this contention [33]. Therefore, one of the reasons
for the seemingly preferential enhancement of the bands associated with
CTAB’s positively charged headgroup may be its close positioning to the
 A.L. Dendramisei al. / SERS studyof CTAB on copper 685

surface. This is supported by the overall band intensity increase observed for
small negative voltages (-40 mV) applied to the copper rod, and the band
intensity decrease observed for small positive voltages ( + 40 mv). The voltage
values are referenced to the open circuit potential which was found to be
-0.037 V (SCE).
The symmetric positioning of the three N+-attached methyl groups is
inferred from the sharpness of the CH, deformation band at 1449 cm-‘, which
is indicative of all three methyl groups having similar environments. Such an
arrangement requires the C-N+ bond formed by the carbon of the long chain
to be nearly perpendicular to the metal surface which would explain nicely the
strength of the C-N+ stretch at 763 cm-‘. Lending support to such reasoning
is the pattern seen in the SERS spectrum of tetramethylammonium iodide
(TMAI) adsorbed on copper [27]. In this case, despite the strength and
sharpness of the C-N+ stretching band seen in the normal Raman spectra of
TMAI in the solid and solution form, it appears weak in the SERS spectrum,
while the CH, deformation at - 1450 cm-’ appears considerably broader than
that for CTAB. This is consistent with the TMA group approaching the surface
such that one of its C, axes is perpendicular to it. For this orientation, no
C-N+ bond is perpendicular to the surface to be strongly enhanced and two of
the methyl groups are in a different environment than the other two, contribut-
ing to the larger width of the CH, deformation band.

3.5. Physisorption or chemisorption?

Having some idea of the headgroup and chain positions with respect to the
metal surface still does not answer the question of CTAB’s mode of adsorp-
tion. However, the absence of any significant band frequency shifts between
the solution and SERS spectra points toward a physisorbed or weakly chemiso-
rbed state. This is also supported by the difficulty of observing the SERS
spectrum of CTAB on copper after the copper rod is removed from the
solution, rinsed with water and dried with nitrogen. Because of the poor
heat-dissipating properties of such a sampling arrangement, the laser beam
would tend to drive the physisorbed species away from the interrogated area,
assuming there was still some adsorbed material left after the rinsing and
drying procedures. In any event, evidence of this kind can only be supportive
and not conclusive, since it is not known whether all surface-enhancing
features survive such treatments.
Adsorption of cationic surfactants may be viewed as a consequence of two
phenomena: (a) their tendency to adsorb at any water interface in order to
position the hydrophobic tail out of bulk water, and (b) their increased
sorption when counter-ions are present on the surface of interest. The open
circuit potentials of deoxygenated 1 x 10e4M solutions of either CTAB or
KBr are -0.037 V (SCE) which are positive of the potentials of zero charge.
686 A.L. Dendramis et al. / SERS study of CTAB on copper

The potentials of zero charge were determined from immersion potentials [34]
and correspond with the known value of -0.17 V (SCE) for Cu in Bra
solution [35]. The open circuit potential is dominated by the CuBr/Cu couple
in opposition to the Cu/Cu,O couple. The CuBr/Cu couple has a standard
potential of +0.027 V (SCE) at [Br-] = 1 x 10-4M. One envisions specific
adsorption of Br- and a negative potential at the inner ‘Helmholtz layer. In this
layer would be lodged the cationic headgroups of the surfactant. The surfac-
tant tails would occupy the next adjacent layer. Meakins, Stevens, and Hunter
place the tails of n-decyltrimethyl ammonium ion within 6.9 A of a mercury
surface with specifically adsorbed Cl- ions [36]. We believe a similar situation
obtains on Cu with CTAB.

3.6. Surface morphology

Much has been said about the role of surface roughness in SERS [37,38].
The subject remains controversial and more relevant experimental data are
needed for understanding its importance. For this reason, and as a reference
point for future work in this area, we proceeded with a morphological
characterization of the surfaces involved.
Scanning Electron Microscopy (SEM) was used to determine the surface
roughness of the copper rod tip used for the SERS experiments. SEM photo-
graphs taken before and after exposure of the copper surface to a 1 X 10e4M
solution of CTAB show significant differences in surface roughness. The
surface, prior to CTAB exposure, was polished with a 0.05 pm alumina
suspension and appeared smooth within 500 A. After exposure to CTAB
followed by rinsing and drying as discussed previously, however, nodules of
diameters up to 1000 A were prevalent throughout the surface. So, even though
no electrochemical pretreatment was employed, surface roughness in the 500 to
1000 A range was present in our experiments. It is not clear what is the cause
of roughness in experiments of this kind, although one can speculate that the
presence of halide anions in solution may be responsible for it. Data from the
corrosion science literature [39,40] appear to be consistent with this notion.

4. Conclusions

The use of SERS has allowed the in situ investigation of CTAB adsorption
on copper. Electrochemical roughness was not found necessary for adequate
band intensity enhancement. Under the conditions of the experiment, the
adsorption process is slow enough to be followed in real time, even with PMT
detection. No structural changes appear to take place with increasing surface
coverage. The rate of adsorption increases as a function of the surfactant
concentration in solution; however, the ultimate amount of surfactant ad-
 A.L. Dendramis et al. / SERS study of CTAB on copper 687

sorbed and its packing/orientation seem to remain unchanged. The bands

corresponding to headgroup vibrations appear to be preferentially enhanced
over those of the long chain, but experiments with selectively deuterated CTAB
will be required for definitive proof of some of the assignments made. When
the “surface selection rule” of the “image field theory” is employed [31], the
data imply a CTAB orientation which places the C-C bonds of the long chain
parallel to the copper surface, the headgroup in close proximity to the surface
and the three methyl groups positioned symmetrically over it. SERS studies of
isotopically labelled long-chain surfactants adsorbed on metals should prove
invaluable in understanding the interactions involved in such systems. They
may also provide important information on the “selection rules” in effect.

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