The infrared spectrum

The vibrations of a polyatomic molecule can be considered as a system of coupled anharmonic oscillators. If there are N atomic nuclei in the molecule, there will be a total of 3N degrees of freedom of motion for all the nuclear masses in the molecule. Subtracting the pure translations and rotations of the entire molecule leaves (3N-6) vibrational degrees of freedom for a non-linear molecule and (3N-5) vibrational degrees of freedom for a linear molecule. These internal degrees of freedom correspond to the number of independent normal modes of vibration. Note that in each normal mode of vibration all the atoms of the molecule vibrate with the same frequency and pass through their equilibrium positions simultaneously. 

The determination of the form and of the frequency of normal modes of molecular vibrations is beyond the scope of this present book. The reader interested in this topic is referred to the relevant books listed in the bibliography. 

Infrared spectroscopy is based on the interaction of electromagnetic radiation with a molecular system, in most cases in the form of absorption of energy from the incident beam. The absorption of infrared light induces transitions between the vibrational energy levels given by Eq. (4.7). As shown in Fig. 4.2, the energy levels of the anharmonic oscillator are not equidistant. 

When a molecule is raised from the ground vibrational state n = 0) to the first excited vibrational state (n = 1), it is said to undergo a fundamental transition. According to Eq. (4.7) the wavenumber of the fundamental transition is given by 

The intensity of an infrared absorption band is proportional to the square of the change in the molecular electric dipole moment p caused by a normal coordinate q  

When infrared radiation of successive frequencies (or wavelengths) is incident on a molecule, some of the radiation frequencies correspond to characteristic frequencies of the molecule, and under such natural resonant conditions energy can be exchanged from one system to another if a coupling mechanism is available. The coupling mechanism in this case is the change in electric dipole moment caused by the vibration of a bond. The scanning of a molecular sample with successive infrared frequencies shows frequency values for which the radiation is absorbed, and these values correspond qualitatively to mechanical vibration frequencies of the molecule. The infrared spectrum is an analysis of the molecular vibrations. 

In an infrared spectrum the amount of radiation absorbed (or transmitted) is plotted as a function of the wavelength. The intensity of radiation of one wavelength transmitted by the sample (/) is related to the intensity incident on this sample (/q), to the path length in the sample (b), and to the concentration of the sample (c) by the equation 

An infrared spectrum can be a plot of either absorbance A or transmittance T versus wavelength or wave number. The convention in this country is that the ordinate scale is usually set up in such a way that absorption peaks appear as valleys in the curve, regardless of whether absorbance or transmittance is plotted on the ordinate. Foreign laboratories often plot spectra with the scale arranged differently, and these appear upside down compared to ours but both types give equivalent information, and one should be familiar with them both. 

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Nevertheless, a molecule possesses sufficient vibrations so that all its frequencies taken together can be used to characterize it. In this sense the infrared spectrum is generally considered to be a molecule s fingerprint."... 

XI-1C) as well as alongside it. The infrared spectrum of CO2 adsorbed on 7-alumina suggests the presence of both physically and chemically adsorbed molecules [3]. 

Infrared Spectroscopy. The infrared spectroscopy of adsorbates has been studied for many years, especially for chemisorbed species (see Section XVIII-2C). In the case of physisorption, where the molecule remains intact, one is interested in how the molecular symmetry is altered on adsorption. Perhaps the conceptually simplest case is that of H2 on NaCl(lOO). Being homo-polar, Ha by itself has no allowed vibrational absorption (except for some weak collision-induced transitions) but when adsorbed, the reduced symmetry allows a vibrational spectrum to be observed. Fig. XVII-16 shows the infrared spectrum at 30 K for various degrees of monolayer coverage [96] (the adsorption is Langmuirian with half-coverage at about 10 atm). The bands labeled sf are for transitions of H2 on a smooth face and are from the 7 = 0 and J = 1 rotational states Q /fR) is assigned as a combination band. The bands labeled... 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Oka T 1992 The infrared spectrum of i-ftin laboratory and space plasmas Rev. Mod. Rhys. 64 1141-9... 

Rosenbaum N H, Owrutsky J C, Tack L M and Saykaiiy R J 1986 Veiocity moduiation iaser spectroscopy of negative ions the infrared spectrum of hydroxide (OH ) J. Chem. Phys. 84 5308-13... 

Figiue 7.12 from Guillot B 1991. A Molecular Dynamics Study of the Infrared Spectrum of Water. The Journal of Chemical Physics 95 1543-1551. 

Fig. 7.12 Experimental and calculated infrared spectra for liquid water. The black dots are the experimental values. The thick curve is the classical profile produced by the molecular dynamics simulation. The thin curve is obtained by applying quantum corrections. (Figure redrawn from Guilbt B 1991. A Molecular Dynamics Study of the Infrared Spectrum of Water. Journal of Chemical Physics 95 1543-1551.)...

Interpretation of spectra. The infrared spectrum of m-hydroxybenzoic acid (solid ground in Nujol) is shown in Fig. A, 7, 1. The more important bands may be interpreted as follows. 

Although no chemical reaction occurs, measurements of the freezing point and infra-red spectra show that nitric acid forms i i molecular complexes with acetic acid , ether and dioxan. In contrast, the infrared spectrum of nitric acid in chloroform and carbon tetrachloride - is very similar to that of nitric acid vapour, showing that in these cases a close association with the solvent does not occur. 

The study of the infrared spectrum of thiazole under various physical states (solid, liquid, vapor, in solution) by Sbrana et al. (202) and a similar study, extended to isotopically labeled molecules, by Davidovics et al. (203, 204), gave the symmetry properties of the main vibrations of the thiazole molecule. More recently, the calculation of the normal modes of vibration of the molecule defined a force field for it and confirmed quantitatively the preceeding assignments (205, 206). 

The distinction between in-plane A symmetry) and out-of-plane (A" symmetry) vibrations resulted from the study of the polarization of the diffusion lines and of the rotational fine structure of the vibration-rotation bands in the infrared spectrum of thiazole vapor. 

Valence Vibrations. pCH and pCD. In the 3100 cm region the infrared spectrum of thiazole shows only two absorptions at 3126 and 3092 cm F with the same frequencies as the corresponding Raman lines (201-4) (Fig. I-IO and Table 1-23). In the vapor-phase spectrum of... 

The infrared and Raman spectra of many alkyl and arylthiazoles have been recorded. Band assignment and more fundamental work has been undertaken on a small number of derivatives. Several papers have been dedicated to the interpretation of infrared spectra (128-134, 860), but they are not always in agreement with each other. However, the work of Chouteau (99, 135) is noteworthy. The infrared spectrum of thiazole consists of 18 normal vibrations as well as harmonic and combination bands. 

Treatment of 2 4 6 tn tert butylphenol with bromine in cold acetic acid gives the compound CigH29BrO in quantitative yield The infrared spectrum of this compound contains absorptions at 1630 and 1655 cm Its H NMR spectrum shows only three peaks (all singlets) at 8 1 2 13 and 6 9 in the ratio 9 18 2 What is a reasonable structure for the compound" ... 

This general behaviour is characteristic of type A, B and C bands and is further illustrated in Figure 6.34. This shows part of the infrared spectrum of fluorobenzene, a prolate asymmetric rotor. The bands at about 1156 cm, 1067 cm and 893 cm are type A, B and C bands, respectively. They show less resolved rotational stmcture than those of ethylene. The reason for this is that the molecule is much larger, resulting in far greater congestion of rotational transitions. Nevertheless, it is clear that observation of such rotational contours, and the consequent identification of the direction of the vibrational transition moment, is very useful in fhe assignmenf of vibrational modes. 

In the infrared, 2-hydroxycyclobutanone has a carbonyl band at 1780 cm in chloroform solution. Kept in nitrogen-filled screw-capped vials in the freezing compartment of a refrigerator, 2-hydroxyoyolo-butanone slowly but completely solidifies as its dimer. The infrared spectrum of the solid in a KBr disk shows no carbonyl. However, a chloroform solution of the solid does show the characteristic 1780 em band, indicating rapid equilibration with the monomer. 

The infrared spectrum (chloroform) shows bands at 2230 (medium strong), 1348, and 940 (medium) cm. The proton magnetic resonance spectrum (chloroform-d) shows absorption at 3 5.73 and 7.33 (AA XX pattern). 

The purity of cyclobutanone was checked by gas chromatography on a 3.6-m. column containing 20% silicone SE 30 on chromosorb W at 65°. The infrared spectrum (neat) shows carbonyl absorption at 1779 cm. - the proton magnetic resonance spectrum (carbon tetrachloride) shows a multiplet at 8 2.00 and a triplet at S 3.05 in the ratio 1 2. 

The infrared spectrum of the l-methoxy-l,4-cyclohexadiene shows the absence of strong aromatic absorption at 1600 cm.the ultraviolet spectrum shows absence of absorption at 270 nm., indicating absence of the conjugated isomer. 

The vibrational motions of the chemically bound constituents of matter have fre-quencies in the infrared regime. The oscillations induced by certain vibrational modes provide a means for matter to couple with an impinging beam of infrared electromagnetic radiation and to exchange energy with it when the frequencies are in resonance. In the infrared experiment, the intensity of a beam of infrared radiation is measured before (Iq) and after (7) it interacts with the sample as a function of light frequency, w[. A plot of I/Iq versus frequency is the infrared spectrum. The identities, surrounding environments, and concentrations of the chemical bonds that are present can be determined. 

The goal of the basic infrared experiment is to determine changes in the intensity of a beam of infrared radiation as a function of wavelength or frequency (2.5-50 im or 4000—200 cm respectively) after it interacts with the sample. The centerpiece of most equipment configurations is the infrared spectrophotometer. Its function is to disperse the light from a broadband infrared source and to measure its intensity at each frequency. The ratio of the intensity before and after the light interacts with the sample is determined. The plot of this ratio versus frequency is the infrared spectrum. 

Define Iq to be the intensity of the light incident upon the sample and I to be the intensity of the beam after it has interacted with the sample. The goal of the basic inftared experiment is to determine the intensity ratio I/Iq as a function of the frequency of the light (w). A plot of this ratio versus the frequency is the infrared spectrum. The inftared spectrum is commonly plotted in one of three formats as transmittance, reflectance, or absorbance. If one is measuring the fraction of light transmitted through the sample, this ratio is defined as... 

The simplicity of the infrared spectrum of solid Cgo (see Fig. 9), which shows four prominent lines at 527, 576, 1183, 1428 cm each with Ti symmetry [4], provides a convenient method for characterizing Cqq samples [4, 88]. The IR spectrum of solid Cqq remains almost unchanged relative to the isolated Ceo molecule, with the most prominent addition being the weak feature at... 

In order to obtain the infrared spectrum of a thin film on a reflecting substrate, a transmission experiment is out of the question since infrared radiation cannot be transmitted through any significant thickness of a reflecting material. Instead,... 

In a 250 ml Erlenmeyer flask covered with aluminum foil, 14.3 g (0.0381 mole) of 17a-acetoxy-3j5-hydroxypregn-5-en-20-one is mixed with 50 ml of tetra-hydrofuran, 7 ml ca. 0.076 mole) of dihydropyran, and 0.15 g of p-toluene-sulfonic acid monohydrate. The mixture is warmed to 40 + 5° where upon the steroid dissolves rapidly. The mixture is kept for 45 min and 1 ml of tetra-methylguanidine is added to neutralize the catalyst. Water (100 ml) is added and the organic solvent is removed using a rotary vacuum evaporator. The solid is taken up in ether, the solution is washed with water and saturated salt solution, dried over sodium sulfate, and then treated with Darco and filtered. Removal of the solvent followed by drying at 0.2 mm for 1 hr affords 18.4 g (theory is 17.5 g) of solid having an odor of dihydropyran. The infrared spectrum contains no hydroxyl bands and the crude material is not further purified. This compound has not been described in the literature. 

The progress of the photolysis can be followed either by observing the disappearance of the typical nitrite bands between 1600 and 1680cm (6.25 and 5.95 ju) in the infrared spectrum or by disappearance of the diphenyl-amine-sulfuric acid spot plate test. 

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