Infrared absorption spectra interpretation

Note added in proof. Kamb, Hamilton, LaPloca and Prakash [J. Chem. Phys. 55, 1934 (1971)] have argued, from the comparison of the infrared absorption spectrum of HDO/H2O ice II and crystal structure data, that there is no correlation between vod and hydrogen bond donor angle. Instead, for this case they establish a correspondence between j>od and 00 separation. This interpretation differs from that offered by VRB for high density HaO(as). 

From the Raman spectrum in aqueous solution the anion ring was considered to be planar (139, 268). On the other hand the infrared absorption spectrum (57) of crystals of the stable form was interpreted in favor of the more probable chair form (36). The only X-ray study of the crystalline hexahydratc (40) published up to the present has proved to be incorrect (212). 

B. Guillot and G. Birnbaum. Theoretical interpretation of the far infrared absorption spectrum in molecular liquids nitrogen. In [45], p. 437. 

The infrared spectrum of oxyphenbutazone in nujol mull is presented in Figure 2. An interpretation of the spectrum is given below. The infrared absorption spectrum of oxyphenbutazone is used as an identification test by the B.P. and U.S.P. 

A spectrum is a graphical representation of how the sample and the light are interacting. Here is an Infrared Absorption spectrum. It shows wavenumbers, which are 1/wavelength v. Transmittance, which is related to absorbance. Chemists learn information about the structure of a compound by interpreting the spectra because each compound has a unique spectra, sort of like a finger print. 

In 1951, Witkop et al. interpreted the infrared spectra of quinol-2-and -4-ones to favor the oxo formulation. Since then, many investigators, especially Mason, have reported that potential a- and y-hydroxy compounds show infrared absorption bands in the vN—H (3500-3360 cm ) and vC—O (1780-1550 cm ) regions of the spectrum and, hence, exist predominantly in the oxo form references to this work appear in Table I. A study of the bands which occur in the NH-stretching region of the infrared spectra of a series of substituted pyrid-2-ones and quinol-2-ones also supported an oxo formulation for these compounds. Detailed band assignments have been published for pyrid-2- and -4-one. Mason has reported that solutions of j8-hydroxy compounds in chloroform or carbon tetrachloride show... 

Earlier studies of 4-aminopyridine 1-oxide were less conclusive. The solid-state infrared spectrum could be interpreted to indicate the existence of both the imino structure and/or, more probably, the amino structure. Comparison of the actual pKa value of 4-aminopyridine 1-oxide wdth the value calculated using the Hammett equation was considered to indicate that the compound existed as such or as an equilibrium mixture with l-hydroxypyrid-4-onimine, the latter possibility being considered the less likely on the basis of resonance and bond energies/ Resonance energy and ultraviolet spectral considerations have been advanced to support the 4-aminopyridine 1-oxide structure/ The presence of an infrared absorption band at... 

The eigenvalues calculated either by the Merrifield or ABO method are nearly identical. As can be seen, this analysis leads to the prediction of a number of low-lying infrared absorption bands for this complex. In a discussion of the structure of the Creutz-Taube ion, I pointed out some time ago (27) that the evidence definitely favors a well-delocalized ground state (6 < 1), and predicted that these infrared bands would, thus, not be observed. In a recent publication, Krausz, et al., report that a search for the bands indeed gave negative results, and withdraw their proposed interpretation of the spectrum (48). 

Another complication arises in the interpretation of absorption spectra. If a molecule vibrates with pure harmonic motion and the dipole moment is a linear function of the displacement, then the absorption spectrum will consist of fundamental transitions only. If either of these conditions is not met, as is usually the case, the spectrum will contain overtones (multiples of the fundamental) and combination bands (sums and differences). Most of these overtones and combination bands occur in the near-infrared (0.8-2.0/un). 

O-H bond. Among such properties a prominent one is the ultraviolet absorption spectrum and the theory may therefore be used for the examination of some of the spectroscopic shifts which accompany the lactam-lactim tautomerization. Much caution must, however, be exercised in this respect. Thus, in a recent paper Kwiatkowski135,137 performed Pariser-Parr-Pople-type calculations on the electronic structure of hydroxypurines, essentially to interpret their ultraviolet spectra. In these calculations he assumed that these compounds exist predominantly in their lactim form, and the results of his calculations, at least for 6- and 8-hydroxypurine, did not seem to contradict this assumption. It is only in the case of the 2-hydroxy isomer that a particularly striking disagreement between theory and experiment led him to admit that this last compound may exist in the lactam form. Calculations carried out for this form gave, in fact, a more satisfactory agreement with experiment.138 As we have seen, unambiguous infrared spectroscopy evidence clearly show s that all three isomers exist essentially in the lactam form. This shows that ultraviolet absorption may provide only very uncertain evidence about the lactam-lactim tautomerism in hydroxypurines and related compounds. 

The Raman spectra are quicker and easier to determine than the infrared absorption spectra because ordinary optical equipment can be used, but frequently they are more difficult to interpret. The quantum restrictions in the two phenomena, particularly for symmetrical molecules, are not always the same, because the Raman spectrum involves an intermediate excited state of the molecule. For this reason, it is desirable to have the data of both Raman and infrared absorption spectra in order to determine completely the rotational and rotational-vibrational energy levels in the molecule. The Raman spectrum can be obtained in some solutions where direct absorption measurements are impossible because the solvent is opaque in the infrared. Aqueous solutions offer a good example of such a case. 

The difficulties of interpretation presented by some of these complexes are well illustrated by the sequence of ferrocene derivatives (VIII to X). The spectrum of VIII shows a near-infrared absorption as expected for a mixed valence complex, but the band has a shoulder, and at low temperatures is resolved into two bands. Complex IX has a well-defined band almost certainly ascribable to intervalence transfer, but complex X with a similar molecular structure has no such... 

The infrared spectrum of l,5-diamino-l,2,4-triazolo[l,5-c]quinazolinium bromide (75) showed two intense absorptions near 1700 cm-1. These absorptions were interpreted, on the basis of deuteration experiments, to be due to v C=N+ coupled with 8 NH2 and other ring modes [79JCS(P2)1708]. 

Figure 1 gives a typical infrared spectrum of lake humic acid. The interpretation of infrared spectra of humic substances is discussed in depth by -MacCarthy and Rice in Chapter 21. The similarity of infrared spectra of humic acids from different lakes suggests a similarity of the aspects of chemical structure that are related to their infrared absorptions. However, infrared spectroscopy is not sensitive enough to uncover minor structural differences among humic acids. In fact, humic acids were separated by organic solvents (chloroform, methylethylketone, methanol, dimethylformamide) into various fractions (Ishiwatari, 1969b, 1973). Infrared spectra of two of these fractions, the chloroform-soluble fraction and the methylethylketone-... 

---