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Raman spectra of single crystals of adipic and sebacic acids and a study of the hydrogen bond vibrations in carboxylic acid dimers

Ananthanarayanan, VS (1964) Raman spectra of single crystals of adipic and sebacic acids and a study of the hydrogen bond vibrations in carboxylic acid dimers. In: Spectrochimica Acta, 20 (2). pp. 197-210.

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Official URL: http://dx.doi.org/10.1016/0371-1951(64)80009-6

Abstract

Raman spectra of single crystals of adipic and sebacic acids have been photographed for the first time using λ 2537 excitation. The spectra have been divided into four regions: (a) internal frequencies; (b) summations and overtones; (c) external vibrations; and (d) low-frequency hydrogen bond oscillations. Tentative correlations have been given for all the internal frequencies and summations and overtones. A series of diffuse weak bands observed in the spectra of both these acids in the not, vert, similar2400–2800 cm−1 have been explained as a superposition of O---H frequencies lowered due to hydrogen bond formation over the summations and overtones of fundamentals mainly in the not, vert, similar1000–1500 cm−1 region. Rotatory type of external oscillations of the two formula units of these molecules in their unit cells have been identified at 76, 99, 118 and 165 cm−1 in adipic acid and 66, 95, 117 and 177 cm−1 in the spectrum of sebacic acid. A brief discussion of the low frequency hydrogen bond vibrations in these acids has been made. Making use of the Lippincott—Schroeder potential and assuming a highly anharmonic potential curve for the hydrogen bond, the vibrational frequencies of the bond have been theoretically evaluated. There is very good agreement between these and the experimental values. The results for adipic acid in cm−1 are: 304 (0 → 1), 270 (1 → 2), 241 (2 → 3), 222 (3 → 4) 201 (4 → 5), 183 (5 → 6). In the case of sebacic acid some of the intermediate and higher transitions are absent in the spectrum recorded by the author. From the above data for adipic acid the dissociation energy of the hydrogen bond was evaluated as 5·9 kcal/mole in fair agreement with the values derived from conventional methods.

Item Type: Journal Article
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Additional Information: Copyright of this article belongs to Elsevier Science.
Department/Centre: Division of Physical & Mathematical Sciences > Physics
Date Deposited: 24 May 2010 08:33
Last Modified: 19 Sep 2010 06:07
URI: http://eprints.iisc.ernet.in/id/eprint/28097

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