/ CHAPTER 2 ; TABLES OF CHARACTERISTIC FREQUENCIES I 2.1. POSITION OF ABSORPTION BANDS Unless otherwise stated the bands usually appear within £10 cm"? of the position shown. The data are mostly for compounds measured as dilute solutions in nonpolar solvents, and the external and internal factors such as solvation, inter- or intra+ molecular hydrogen-bonding, electric effects of nearby groups, steric strain, and other ste effects will shift the bands from their normal positions. Bands that are not practically useful are written in italics. Some have been completely omitted, e.g., skeletal vibration in the finger-print region. 2.2. INTENSITY The infrared absorption intensities still cannot be expressed in terms of a uni~ versal constant, because the band width is of the same order as the slit width, which causes the measured optical density to be influenced strongly by the slit width. ‘Therefore, in qualitative organic chemistry the intensity is usually expressed as vs (very strong), s (strong), m (medium), w (weak), etc. However, these notations, which are merely given subjectively to a band by glancing at the spectrum in question, do not represent the true intensity of a band. In the following tables the apparent molecular coefficient <* has been given whenever possible, besides the conventional notations. It is defined as: 1 Ty 4 onal), : apparent molecular absorption coefficient €: concentration, moles per liter 1: cell thickness, cm Tp and T: intensity of entering and transmitted light, Measurements are not made under strictly monochromatic conditions because of the slit width, Accordingly, logy (To/T). is the apparent optical density obtained when the instrument is set to awave- number of », and it is not the true absorptivity involved in the Beer-Lampert rule. The apparent integrated area is defined as: B=2.303f 7Methods for converting apparent intensities into true molecular absorption coefficients and integrated areas (A) are described in reference (1). The = values given in the tables give only a rongh idea of the intensities sine the values vary according to the instrument, slit widtis, and other experimental condi tions, and the difference between ¢ and = is also variable (¢ is larger than « by 0 ~20%). Even under identical instrumental conditions the « values may vary as much as 10% according to the sample concentration. An example has also been reported in which the « was 1430 with a sodium ebloride prism whereas it was 1890 with a calcium fluoride prism. "The © values are hence still in quite an unsatisfactory state but conventional notations are even more inconsistent. 2.3. ASSIGNMENTS A molecule of n atoms has 3n degrees of freedom, three of which are assigned to translational, another three to rotational (two in linear molecules such as acetylene), and the remaining 32-6 (3-5 if linear) to vibrational motions. ‘These various vibr tions (fundamental vibrations) absorb, respectively, the infrared beam at characteristic frequencies and give rise to absorption bands. However the number of absorption, bands does not coincide exactly with the number of fundamental vibrations. Thus, if the vibration dees not induce any change in the polarity of the entire molecule, the vibra- tion will not absorb the infrared energy and the number of infrared peaks will be de- creased accordingly. For example, the vibration of the central C=C bond of the ethylene molecule will not absorb infrared energy (infrared inactive). Fundamental vibration bands can be divided into those caused by stretching vibrations and those caused by deformation vibrations. Vibrations of the methylene group are shown as an example: : Ne ee ane er hs Pot ee A [ IP asymmetric symmetric stissoring. wagging twisting, rocking vasCHe »sCHs CH, Biretching vibsation ‘bending (or deformation) vibration Vibrations of the methylene group. (the + and —signs denote vibrations in the direction perpendicular to the paper). Note: Particular asymmetric stretching vibrations in which two bonds move in the opposite direction, such as the asymmetric stretching of the methylene group, are also called antisymmetric stretching vibrations. Other groups having similar arrangements of atoms, eg, HL 0 0 : n€ sot ke AG Ko & } amino nitro: carboxylate also possess fundamental vibrations corresponding to those of the methylene group. In certain cases, vibrations other than the normal ones will appear. 18+ Tables of characteristic frequenciesOvertone: Overtones having twice the frequency of the normal vibration will occa- sionally be observed as weak bands. For instance, the overtone of the carbonyl 1715 cm™ absorption may appear around 3430.cm~', and may be confused with the hydroxyl absorption, ‘Combination tone: ‘These are weak bands occasionally appearing at frequencies that are the sum or difference of two or more fundamental bands. Thus, fundamental bands at x and y em“ may give rise to weak bands at (x+y) or (r—y) em" ‘The following phenomena also occur in the spectra, ‘Coupling: Very often a 1:1 correspondence between a bond vibration and an ab- sorption band cannot be assumed. This coupling phenomenon occurs when two bonds of the same symmetry are closely located within the molecule, the respective bands are strong, and the absorptions oceur in the same region. It must be borne in mind that the coupling will cause bands to shift outside the characteristic frequency range. However, there are cases in which the coupled bands themselves constitute useful characteristic absorption bands, such as is encountered in acids and amides. Fermi resonance: When an overtone or combination band is located near a fundamental frequency, the band intensity of the former may be anomalously enhanced or bands may be split (w-butyl vinyl ether, @). ‘This coupling between an overtone or com= bination band and a fundamental band is called the Fermi resonance; the two levels also have to be of the same symmeti Reference [1] RN. Jonesand C. Sandorfy, “ Chemical Applications of Spectroscopy,” p. 271, (1956) Interscience. latsui, ‘* IR Spectra” Vol. 3, p. 151 (1958). . Kuratani and R. Mineyasu, ibid. Vol. §, p. 1 (1959) K. S. Sheshadri and R. N. Jones, “‘The Shapes and Intensities of Infrared Absorption Bands A Review,” Specirochimica Acta, in press (2] GD. Mealtins and R. J. Moss, J. Chem. Soe. 993 (1959). Abbreviations aliph, aliphatic H-bonding: hydrogen-bonding arom. aromatic , primary assoc. associated resp. respectively 7 asym. asymmetric 5 secondary conj. conjugation sad. saturated corresp. corresponding sym symmetric freq. frequency of Frequencies a tertiary unsatd, unsaturated Tables of characteristic frequencies ~ 19