JOURNAL OF RAMAN SPECTROSCOPY, VOL.

29, 143È148 (1998)

Three Distinct Geometries of Surface-Adsorbed
Carboxylate Groups
Jung Sang Suh* and Jurae Kim
Department of Chemistry Education, Seoul National University, Seoul 151-742, Korea

The surface geometry of carboxylate groups was studied by analysis of the SERS spectra of aromatic carboxylic
acids adsorbed on silver colloid surfaces. Three distinct types of carboxylate group surface geometry were identiÐed. In the Ñat geometry, the CO — group interacts with the surface through its p-electrons, and the m (COO—)
2
s
band is very strong whereas the d(COO—) band is very weak. In the two-legged standing up geometry, the CO —
2
group is adsorbed through both of its oxygen atoms, but tilted with respect to the surface. The relative intensity of
the d(COO—) band with respect to the m (COO—) band increases as the tilt of the carboxylate group to the surface
s
increases. Finally, in the one-legged geometry, only one oxygen of the CO — group is adsorbed on the surface and
2
the d(COO—) band is stronger than the m (COO—) band. ( 1998 John Wiley & Sons, Ltd.
s
J. Raman Spectrosc. 29, 143È148 (1998)

INTRODUCTION
Surface-enhanced Raman spectroscopy (SERS) has been
used to determine the orientation of molecules adsorbed
on certain surfaces.1h4 The SERS spectra of many carboxylic acids5h14 have shown that the acid is adsorbed
on the surface as the carboxylate ion. In the SERS
spectra of aromatic carboxylic acids, there are two distinct SERS bands related to the vibrational modes of
the carboxylate group. One is the l (COO~) band near
s
1390 cm~1 and the other is the d(COO~)
band near 850
cm~1. The relative intensity of these two bands in SERS
spectra is di†erent from adsorbate to adsorbate, which
may reÑect di†erences in the surface geometry of the
carboxylate group. However, there has been no detailed
determination of this surface orientation. In this work,
we observed the SERS spectra of isomeric pyridinecarboxylic acids, o- and p-aminobenzoic acids, thiosalicylic and 4-methylthiobenzoic acids. From the
analysis of these spectra, we found at least three types of
carboxylate group surface geometry.

EXPERIMENTAL
Silver sols were prepared as described previously.12
BrieÑy, 60 ml of 2 ] 10~3 M sodium borohydride solution was mixed with 22 ^ 2 ml of 1 ] 10~3 M silver
nitrate solution.
The adsorbate was introduced to the colloid by dissolving the acids in distilled water. SERS spectra were

* Correspondence to : J. S. Suh, Department of Chemistry Education, Seoul National University, Seoul 151-742, Korea.
Contract/grant sponsor : KOSEF.
Contract/grant sponsor : Center for Molecular Science.
Contract/grant sponsor : POSCO Research Fund of Seoul National
University.
CCC 0377È0486/98/020143È06 $17.50
( 1998 John Wiley & Sons, Ltd.

excited with 20 mW of focused radiation of 514.5 nm
from an argon ion laser (Lexel Model 3000). The SERS
spectra were recorded using a Spex 1887C Triplemate
spectrometer equipped with a multi-channel chargecoupled device (CCD) detector.

RESULTS AND DISCUSSION
The SERS spectra of the isomeric pyridinecarboxylic
acids to picolinic, nicotinic and isonicotinic acid to
adsorbed on a silver sol surface are shown in Fig. 1,
those of o- and p-aminobenzoic acid in Fig. 2 and those
of thiosalicylic and 4-methylthiobenzoic acid in Fig. 3.
The SERS spectra of all these compounds are very
similar to those reported previously.7h14
In Fig. 1, the strong bands in each spectrum near
1385 and 850 cm~1 are assigned to l (COO~) and
d(COO~), respectively. The l bands s of the three
isomers picolinic, nicotinic and 1isonicotinic acid are at
1016, 1032 and 1012 cm~1, respectively.7h10 The strong
band near 1600 cm~ is assigned to l . The band near
8a the strong back3070 cm~1 is due to CH stretching and
ground near 3000 cm~1 is due to H O vibrations.
2
The SERS spectra of o- and p-aminobenzoic
acid are
very di†erent from each other. There is a distinct CH
stretching band near 3060 cm~1 in the SERS spectrum
of o-aminobenzoic acid [Fig. 2(a)], whereas no CH
stretch is observed for p-aminobenzoic acid [Fig. 2(b)].
Similarly, there is a very strong band at 803 cm~1 in
Fig. 2(a) but there is no strong band near 800 cm~1 in
Fig. 2(b). This band has been assigned as l , but it
10a
may borrow some intensity from the l mode.11
The
1
band near 1600 cm~1 is assigned to l and the asym8a cm~1. In Fig.
metric NH bend is observed near 1135
2
2(b), the strong bands at 1513 and 1452 cm~1 are due to
l
and l , respectively.12 The l (COO~) band near
19a cm~119bis strong but the d(COO~)
s
1380
band near 850
cm~1 is weak.
Received 11 January 1997
Accepted 15 September 1997

13 The l (COO~) and d(COO~) bands are s and 843 cm~1. (b) nicotinic and (c) isonicotinic acid adsorbed on an aqueous silver sol. relatively weak at 1380 In the SERS spectrum of 4-methylthiobenzoic acid [Fig. where the l (COO~) band is very s is weak. S. This variation can probably be interpreted in terms of di†erent surface geometries of the CO ~ group. The band at 2920 cm~1 is due to l of the methyl group. The spectra shown in Figs 1È3 are divided into three groups according to the relative intensity of these two bands. there were no bands corresponding to SH vibrational modes. respectively.144 J. It is known that the aromatic CH stretching vibration appears distinctly when the ring is oriented perpendicular to or tilted with respect ( 1998 John Wiley & Sons. The hydrogen of the SH 18b of thiosalicylic 13 group acid is known to be dissociated on the surface. 3(b)]. SERS spectra obtained from (a) picolinic. the pyridine ring of picolinic acid is oriented more perpendicular to the surface than its two isomers. to the surface. excited with 514. the strong bands at 1037 and 1120 cm~1 are assigned to l and l . In the solid. In the SERS spectrum of thiosalicylic acid [Fig. respectively. Therefore. The relative intensity of the l (COO~) and d(COO~) s bands is di†erent from spectrum to spectrum. respectively. Vol..14 The l (COO~) s band is very 8a strong at121383 cm~1 while the d(COO~) band is relatively weak at 836 cm~1. Hence the pyridine and benzene rings of these acids are not parallel to the surface. l(SH) and b(SH) bands are at 2580 and 914 cm~1. The absolute intensity of these bands may be2 a†ected by the laser power used. The l band of picolinic acid is stronger than that of its twoCHisomers. and does not appear at all with parallel orientation. includes the strong while the d(COO~) band spectra of p-aminobenzoic.5 nm radiation from an argon ion laser. The Ðrst group.4 There is clearly an aromatic CH stretching band near 3070 cm~1 in the SERS spectra of all three pyridinecarboxylic acids and o-aminobenzoic acid. This means that CH is not broken on the surface under the SÈCH bond 3 our experimental conditions. SUH AND J. the local 2 electric Ðeld strength on the surface and so on. 29. Ltd. surface concentration of adsorbate. The relative intensity of the aromatic CH stretch in the SERS spectrum provides a clue to the surface geometry of the molecule. 3(a)]. KIM Figure 1. Raman Spectrosc. distance of the CO ~ group from the surface. the strong bands at 1584 and 1081 cm~1 are assigned to l and l . 4-methylthiobenzoic and oJ. respectively.3.13 In the SERS spectrum. 143È148 (1998) .

involving the n-electron of the carboxylate group to the surface. where the sists d(COO~) band is stronger than the l (COO~) band. having l (COO~) and d(COO~) bands of similar intensity. s includes isonicotinic. the benzene ring. These planar molecules are adsorbed Ñat on the surface since there is no distinct aromatic l band in their SERS spectra. For the 4-methylthiobenzoate ion.15 For the picolinate ion. we should consider two possible geometries of the carboxylate group on surface. the two carboxylate groups are rotated ca. Vol. To be adsorbed by all three atoms on the surface simultaneously. The second group. nicotinic and thiosalicylic acids. Raman Spectrosc. but for (a) o .4 The carboxylate group and the N atom of the pyridine ring can be adsorbed strongly on the surface and..and (b) p -aminobenzoic acid. This geometry of the adsorbed picolinate ion. As Fig. In this case. 4. they may be adsorbed on the surface simultaneously. since they are in adjacent positions. The proposed surface CH geometries of paminobenzoate and 4-methylthiobenzoate ions. band. p-Aminobenzoic and 4-methylthiobenzoic acid belonging to the Ðrst group are para-substituted compounds and the carboxylate group in each molecule does not encounter any steric hindrance. The third group.3. the CO ~ group should be rotated some 2 degrees from the plane of the pyridine ring. some steric hindrance is expected between the CO ~ 2 and the non-bonding electron pair of the pyridine ring J. 1. There is a strong l band at 3072 cm~1. carboxylate group and sulfur atom may be coplanar whereas the methyl group protrudes from this plane. For thiosalicylic acid. 143È148 (1998) . suggested by Chattopadhyay et al.10 seems very unstable because only one oxygen of the carboxylate group is adsorbed on the surface. the pyridine ring should be standing up on the surface. cons of picolinic acid alone. If the plane of the carboxylate group in the picolinate ion is coplanar with the pyridine ring. Ltd. It is known that in crystalline phthalic acid. are shown in Fig. aminobenzoic acid. Picolinic acid belongs to the second group. both bands are very weak. only one oxygen atom of the carboxylate group and the N atom of the pyridine ring can be adsorbed on the surface.. 29. 33¡ with respect to the benzene ring due to steric hindrance.GEOMETRIES OF SURFACE-ADSORBED CARBOXYLATE 145 Figure 2. the benzene ring and carboxylate group may be coplanar. Therefore. To show a strong l CH CH ( 1998 John Wiley & Sons.

Ltd. the ring and. including benzoic acid. In the SERS spectrum of o-aminobenzoic acid [Fig. From these results. the anion form is dominant. To have a distinct CH stretching band. The proposed surface geometry (“two-legged standing upÏ geometry) is shown in Fig. there is a distinct CH stretching band near 3060 cm~1. the relative intensity of the d(COO~) band is stronger. S.. Thiosalicylic acid is an ortho-substituted comJ. nicotinic and thiosalicylic acid. to a lesser extent.146 J. at 1380 cm~1 with respect to the d(COO~) band at 852 cm~1 is very strong to be classiÐed in the Ðrst group. although in the latter case the peak intensities are much weaker. The proposed surface geometry of o-aminobenzoate ion is shown in Fig. KIM Figure 3. rotation of the carboxylate group from the pyridine ring is distinctly possible. Note that in this geometry. The third group is characterized by the intensity of the d(COO~) band being stronger than that of l (COO~). 4. but the relative intensity of the l (COO~) band s ( 1998 John Wiley & Sons. Raman Spectrosc. In a tilted geometry. the l (COO~) s band is strong whereas the d(COO~) band is weak. 4. The relatively weak d(COO~) band in the spectrum of oaminobenzoic acid is then interpreted as a slight tilt of the carboxylate group from the surface. the CO ~ 2 group are tilted up with respect to the surface.) With a rotated CO ~ group conÐguration. In the Ñat down geometry of the carboxylate group. Vol. SUH AND J. 143È148 (1998) . but for (a) thiosalicylic and (b) 4-methylthiobenzoic acid. 2(a)]. As Fig. We can clearly see this situation in the SERS s spectra of isonicotinic. The strong l band at CH up on 3072 cm~1 is consistent with the ring standing the surface. it may be inferred that the relative intensity of the d(COO~) band with respect to the l (COO~) band increases as the tilt of the s carboxylate group to the surface increases. exist in a stable dimeric form owing to very strong intermolecular hydrogen bonding. Therefore. 29. hence the conÐguration of the carboxylate group cannot be deduced from the solid-state structure. nitrogen atom because they are both negatively charged and in adjacent positions. the pico2 linate ion can be adsorbed on the surface in a standing up geometry through the non-bonding electron pairs of the pyridine ring nitrogen atom and the two oxygen atoms of the carboxylate group. the benzene ring should be tilted with respect to the surface. 1. (It is well known16 that all carboxylic acids. On the surface.

Therefore. The carboxylate group of p -aminobenzoic and 4-methylthiobenzoic acid is adsorbed flat on the surface through its n-electrons and that of picolinic acid is tilted with respect to the surface by adsorption through both of its oxygen atoms. 1032 and 1012 cm~1. Ltd.9 Adsorption on the positively charged1 metal surface seems to have an e†ect similar to that observed with the zwitterion. the wavenumbers of the l mode of picolinic. Nicotinic acidCHis a meta-substituted compound. the zwitterion form of that of the anion. Evidence for the interaction strength is found in the wavenumber shift of the l mode. they are 1016. yielding corresponding blue shifts of 14. 4-methylthiobenzoic. 1 and 6 cm~1. On a surface.2 It appears that the benzene ring is adsorbed almost Ñat on the surface since there is no signiÐcant l band. It has a planar structure and therefore it is expected to be adsorbed Ñat on the surface.. A Ñat down geometry is isonicotinic acid was proposed by Chattopadhyay et al. isomeric pyridinecarboxylic acids exist in the form of cations. o -aminobenzoic and picolinic acid. shown in Fig. in a Ñat CH down geometry. 5. picolinic acid has a l of 1011 cm~1. 1(c)]. as shown in Fig. For sol-1 vated anions. Anyway. The proposed surface geometries of p -aminobenzoic. In the proposed adsorption geometries. 29. To increase this interaction. 5. it is difficult for the non-bonding electron pair of the pyridine ring nitrogen atom to interact with the surface. The resulting adsorption geometry. Vol. nicotinic and isonicotinic acid are 11002. relatively large and in adjacent positions. the pyridine ring may tilt with respect to the surface. In the SERS spectra. pound and on the surface the hydrogen of the SH group is dissociated. In order to reduce the steric hindrance. The carboxylate group of o -aminobenzoic acid is less tilted than that of picolinic acid. strong steric hindrance is expected between the S~ and CO ~ groups because 2 they are both negatively charged.10 In this geometry. In this of the CO ~ group can be adsorbed on the surface 2 ~ group is rotated from the plane of the since the CO benzene ring. 5. the interaction of the pyridine ring with the surface through the nonbonding electron pair of the nitrogen atom should be greater for picolinic acid than either nicotinic or isonicotinic acid. only one of the oxygen atoms 3060 cm~1. 143È148 (1998) . respectively. a Ñat down geometry reduces the interaction of the non-bonding electron pair of the nitrogen atom with the surface. Isonicotinic acid is a para-substituted compound. The proposed slightly tilted surface geometry of the pyridine ring is supported by the observed weak l band at 3070 cm~1. in which three possible adsorption groups (the pyridine ring. CO ~ group and nitrogen atom) simultaneously interact 2with the surface. 1 In aqueous solution. Raman Spectrosc. no l band is expected in the SERS spectrum but there is CH a distinct l band at 3070 cm~1 [see Fig. the pyridine ring of picolinic acid adsorbed on the surface is more strongly tilted from the surface than that of either nicotinic or isonicotinic acid. such a tilt would decrease the interaction between both the CO ~ group and the pyridine ring with the surface. We 2proposed that the CO ~ group is rotated from the plane of the ring in order2 to allow adsorption by one carboxylate oxygen in order to stabilize this tilt. only a very weak shoulder at CH case.2The proposed adsorption geometry (“oneleggedÏ geometry) is shown in Fig. depending on the pH of the solution. The wavenumber of the l mode of the zwitterion is higher than 1 For example. is ( 1998 John Wiley & Sons. the plane of CO ~ group is probably rotated from the molecular plane.GEOMETRIES OF SURFACE-ADSORBED CARBOXYLATE 147 Figure 4. The wavenumber of the l mode is increased by adsorption on the surface. We therefore propose a similar surface geometry to that of isonicotinic acid. For J. As with isonicotinic acid. However. the anionic form is dominant. 1031 and 1006 cm~1. zwitterions or anions. respectively. Therefore.

Kim and M. S. Spectrochim . B. Soc . 598 (1987). J. Kim. KIM Figure 5. This is also supported by the l band near 3070 cm~1 in their SERS spectra. Part A 49. Chem . Kim and M. S. 15.. Raman Spectrosc . Moskovits of the University of Toronto for the use of laboratory facilities. The carboxylate group is adsorbed on the surface through only one of its oxygen atoms. SUH AND J. 2764 (1974).. J. When the CO ~ group is adsorbed Ñat on the surface through n2 electrons. 2. Mol . Finally. M. Phys . Plieth. Derissen. 25 (1994). 11. J . Kwon. 344. 7. Phys . 14. 1255 (1963) . 6327 (1988). 22. Park. Struct . When the CO ~ group is tilted on the 2 surface by adsorption through both of its oxygen atoms. J. 107. Surf . Kim and M. ELBS. J . 91. J . J . M. 77. 5. K. J . the d(COO~) band is stronger than the l (COO~) band. M. Raman Spectrosc . E. 3. Panagiotakis and W. 4. S. J. Moskovits. the l (COO~) band is much stronger than the s d(COO~) band. J. B. The weaker interaction would be consistent with surface geometries that are less tilted from the surface. As Fig. D. Ruasse. Creighton. J. the wavenumber shifts of the l mode by adsorption on the surface are relatively small. Moskovits and J. Chem . S. nicotinic and isonicotinic acid. the l (COO~) and d(COO~) bands have similar intensities s but the l (COO~) band is stronger than the d(COO~) band. Moskovits and J. Pofahl. but for thiosalicylic. 12. S. Spectrochim . Chem . nicotinic and isonicotinic acid. Raman Spectrosc. 9. Struct . Organic Spectroscopy . REFERENCES 1. Lee. Schifferdecker. 99. 124. S. S. J . s Acknowledgement We thank Professor M. M. from the analysis of the SERS spectra we have found that there are three types of surface geometry for the carboxylate group of aromatic carboxylic acids adsorbed on a silver sol surface. Levi and E. J . Chem . 811 (1991). W.148 J. S. ( 1998 John Wiley & Sons. 4408 (1982). Park. 13. sThe relative intensity of the d(COO~) band with respect to the l (COO~) band becomes stronger as the carboxylate sgroup is more strongly tilted. Pantigny. 737 (1993). As discussed previously. Phys . Mol . 4. Sci . J. J . Kim and M. S. Suh and K. Moskovits. S. Phys . Kim. Suh. Acta Crystallogr . K. L. 24. F. 8. Chem . Soc . Suh. The lCH band of picolinic acid is stronger than that of nicoCH of isonicotinic acid. S. J. Ltd. A. S. Wentrup-Byrye. 6826 (1985). P. Chem . W. Kim. 328. 92. Brahma. Am . Acta 19. Suh and M. Barthelmes. J. 143È148 (1998) . Chem . 318. J . K. 6. 195 (1995). Kemp. Michaelian. J . Aubard. Maier and O. 1540 (1983). when the carboxylate group is adsorbed through only one of its oxygen atoms. S. B 30. 589 (1993). G. DiLella and M. J . 29. M. This work was supported by the KOSEF through the Center for Molecular Science and POSCO Research Fund of SNU. J . Am . 4711 (1986). J. Bagnasco. Phys . Lee. S. Suh. Moskovits. when In summary. 7075 (1995). Chattopadhyay and S. Mol . M. Hong Kong (1986). 87. 108. 10. Kim. Sect . 169 (1994). H. K. the tinic l band of the benzene or pyridine ring is stronger CH the ring is more tilted from the surface. 209 (1983). Struct . Acta . K. G.1 This may reÑect the fact that their interaction with the metal surface through the nitrogen atom is weaker than that of picolic acid. S. M. Y. Vol. 16.