H stretches

Compounds containing a hydroxyl group (OH) have a strong very broad absorption in the 3,600-2,500 cm region of the spectrum. The most common examples are the alcohols and the carboxylic acids. The combination of a broad 3,600-2,500 cm band with a 1,700 cm peak often indicates a carboxylic acid (or amide — keep reading). 

The N-H stretch in amines occurs in the Scime general region (3,500-3,100 cm ) as the hydroxyl group however, the intensity tends to be less. 

In addition, primary amines usually have two bands. The observation of a 3,500-3,100 cm band with a 1,700 cm peak is often indicative of an amide — or carboxylic acid. (If you ve been paying attention, you saw that coming  

Nearly every organic compound has one or more Ccirbon-hydrogen bonds. For this reason, the C-H stretch isn t as useful as you might think. Some guidelines are helpful  

1 The C-H stretch for hydrogen bound to an sp hybridized carbon is in the 3,000-2,850 cm region. 

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Variational RRKM theory is particularly important for imimolecular dissociation reactions, in which vibrational modes of the reactant molecule become translations and rotations in the products [22]. For CH —> CHg+H dissociation there are tlnee vibrational modes of this type, i.e. the C—H stretch which is the reaction coordinate and the two degenerate H—CH bends, which first transfomi from high-frequency to low-frequency vibrations and then hindered rotors as the H—C bond ruptures. These latter two degrees of freedom are called transitional modes [24,25]. C2Hg 2CH3 dissociation has five transitional modes, i.e. two pairs of degenerate CH rocking/rotational motions and the CH torsion. 

Huang Z S, Jucks K W and Miller R E 1986 The vibrational predissociation lifetime of the HF dimer upon exciting the free-H stretching vibration J. Cham. Phys. 85 3338-41... 

At 321 mn there is a vibronic origin marked This has one quantum of v, the antisynnnetric C-H stretching mode, in the upper state. Its intensity is induced by a distortion along This state has B2 vibrational symmetry. The direct product of B2 and A2 is B, so it has B vibronic syimnetry and absorbs x-polarized light. One can also see a 4 6,, vibronic origin which has the same syimnetry and intensity induced by... 

Ulness D J, Stimson M J, Kirkwood J C and Albrecht A C 1997 Interferometric downconversion of high frequency molecular vibrations with time-frequency-resolved coherent Raman scattering using quasi-cw noisy laser light C-H stretching modes of chloroform and benzene J. Rhys. Chem. A 101 4587-91... 

Figure Bl.22.3. RAIRS data in the C-H stretching region from two different self-assembled monolayers, namely, from a monolayer of dioctadecyldisulfide (ODS) on gold (bottom), and from a monolayer of octadecyltrichlorosilane (OTS) on silicon (top). Although the RAIRS surface selection rules for non-metallic substrates are more complex than those which apply to metals, they can still be used to detemiine adsorption geometries. The spectra shown here were, in fact, analysed to yield the tilt (a) and twist (p) angles of the molecular chains in each case with respect to the surface plane (the resulting values are also given in the figure) [40].

Figure Bl.22.6. Raman spectra in the C-H stretching region from 2-butanol (left frame) and 2-butanethiol (right), each either as bulk liquid (top traces) or adsorbed on a rough silver electrode surface (bottom). An analysis of the relative intensities of the different vibrational modes led to tire proposed adsorption structures depicted in the corresponding panels [53], This example illustrates the usefiilness of Raman spectroscopy for the detennination of adsorption geometries, but also points to its main limitation, namely the need to use rough silver surfaces to achieve adequate signal-to-noise levels.

Figure C2.18.7. The integrated absorbance of tire Si-Cl stretching vibration at 625 cm and tire SiO-H stretching vibration at 3740 cm as a function of time during tire (A) SiCl and (B) H2O half-reactions at 600 K and 10 Torr. Reproduced from [95].

Figure C3.5.11. IR-Raman measurements of vibrational energy flow tlirough acetonitrile in a neat liquid at 300 K, adapted from [41], An ultrashort mid-IR pulse pumps the C-H stretch, which decays in 3 ps. Only 1% of the energy is transferred to the C N stretch, which has an 80 ps lifetime. Most of the energy is transferred to the C-H bend plus about four quanta of C-C=N bend. The daughter C-H bend vibration relaxes by exciting the C-C stretch. The build-up of energy in the C-C=N bend mirrors the build-up of energy in the bath, which continues for about 250 ps after C-H stretch pumping.

An ultrashort mid-IR pulse excited a C-H stretching vibration (-3000 cm ) of neat acetonitrile at 300 K. The loss of C-H stretching energy occurred in 3 ps. Only 1% of that energy was transferred to the C N stretch (2250 cm ), where it remained for -80 ps. Most of the energy was lost from the C-H stretch by the process,... 

Accuracy, however, in biomolecular trajectories, must be defined somewhat subjectively. In the absence of exact reference data (from experiment or from an analytical solution), the convention has been to measure accuracy with respect to reference trajectories by a Verlet-like integrator [18, 19] at a timestep of 1 or 0.5 fs (about one tenth or one twentieth the period, respectively, of the fastest period an 0-H or N-H stretch). As pointed out by Deufihard et al. [20], these values are still larger than those needed to... 

The smaller the value of n (the resonance order), the larger the timestep of disturbance. For example, the linear stability for Verlet is uiAt < 2 for second-order resonance, while IM has no finite limit for stability of this order. Third-order resonance is limited by /3 ( J 1.72) for Verlet compared to about double, or 2 /3 (fa 3.46), for IM. See Table 1 for limiting values of wAt corresponding to interesting combinations of a and n. This table also lists timestep restrictions relevant to biomolecular dynamics, assuming the fastest motion has period of around 10 fs (appropriate for an O-H stretch, for example). 

Band 3, 3-93y. (2548 cm. ). This absorption is characteristic of carboxylic acids and is due to the 0—H stretching absorption in the reson-ance-stabUised dimer. (Carboxylic acids generally exist as dimers in the solid state and in all but very dilute solutions.)... 

In a symmetric top molecule such as NH3, if the transition dipole lies along the molecule s symmetry axis, only k = 0 contributes. Such vibrations preserve the molecule s symmetry relative to this symmetry axis (e.g. the totally symmetric N-H stretching mode in NH3). The additional selection rule AK = 0... 

In addition to sp C—H stretching modes there are other stretching vibrations that appear at frequencies above 3000 cm The most important of these is the O—H stretch of alcohols Figure 13 34 shows the IR spectrum of 2 hexanol It contains a broad peak at 3300 cm ascribable to O—H stretching of hydrogen bonded alcohol groups In... 

The S—H stretching frequency of thiols gives rise to a weak band m the range 2550-2700 cm ... 

Infrared The absorptions of interest m the IR spectra of amines are those associated with N—H vibrations Primary alkyl and arylammes exhibit two peaks m the range 3000-3500 cm which are due to symmetric and antisymmetric N—H stretching modes... 

These two vibrations are clearly visible at 3270 and 3380 cm in the IR spectrum of butylamine shown in Figure 22 la Secondary amines such as diethylamme shown m Figure 22 7i> exhibit only one peak which is due to N—H stretching at 3280 cm Ter tiary amines of course are transparent m this region because they have no N—H bonds... 

FIGURE 22 7 Portions of the IR spectra of (a) butyl amine and (b) diethylamme Primary amines exhibit two peaks due to N—H stretch mg m the 3300 to 3350 cm region whereas secondary amines show only one... 

Section 22 19 The N—H stretching frequency of primary and secondary amines appears m the infrared m the 3000-3500 cm region In the NMR spectra of amines protons and carbons of the type H—C—N are more shielded than H—C—O... 

Infrared The IR spectra of phenols combine features of those of alcohols and aro matic compounds Hydroxyl absorbances resulting from O—H stretching are found m the 3600 cm region and the peak due to C—O stretching appears around 1200-1250 cm These features can be seen m the IR spectrum of p cresol shown m Figure 24 3... 

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