Factors Determining Vibrational Frequencies

According to Eq. (1-26), the vibrational frequency of a diatomic molecule is given by 

the vibrational frequency (observed) has been replaced by coe (Eq. (1-30)) in order to obtain a more accurate force constant. Using the unit of millidynes/A (mdyn/A) or 105 (dynes/cm) for K, and the atomic weight unit (awu) for /r, Eq. (1-41) can be written as 

For H35C1, a)e = 2,989cm 1 and n is 0.9799. Then, its K is 5.16 x 105 (dynes/cm) or 5.16 (mdyn/A). If such a calculation is made for a number of diatomic molecules, we obtain the results shown in Table 1-3. In all four series of compounds, the frequency decreases in going downward in the table. However, the origin of this downward shift is different in each case. In the H2 HD D2 series, it is due to the mass effect since the force constant is not affected by isotopic substitution. In the HF HC1 HBr HI series, it is due to the force constant effect (the bond becomes weaker in the same order) since the reduced mass is almost constant. In the F2 Cl2 Br2 I2 series, however, both effects are operative the molecule becomes heavier and the bond becomes weaker in the same order. Finally, in the N2 CO NO 02, series, the decreasing frequency is due to the force constant effect that is expected from chemical formulas, such as N=N, and 0=0, with CO and NO between them. 

It should be noted, however, that a large force constant does not necessarily mean a stronger bond, since the force constant is the curvature of the potential well near the equilibrium position, 

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The fitted and calculated vibrational frequencies and normal mode composition factors corresponding to the 17 most important NIS bands are presented in Table 5.9. It is evident that the vibrational peaks in the calculated NIS spectrum are typically 0-30 cm lower than to the experimental values. In the calculated NIS spectra, there are two small peaks at 635 and 716 cm (Fig. 5.14b) that are not visible in the experimental spectrum. According to the normal mode calculations these are Fe-N-N and Fe-O-C deformation vibrations. Small admixtures of Fe-N and Fe-O stretching modes account for the calculated nonzero normal mode composition factors. Although the calculated relative intensities are slightly above detection limit dictated by the signal-to-noise ratio, they are determined by values of pea which are very small (0.028 and 0.026 for the peaks at 635 and 716 cm ). They must be considered to be within the uncertainties of the theoretical... 

Among the various methods, the B3-LYP based DFT procedure appears to provide a very cost-effective, satisfactory and accurate means of determining the vibrational frequencies. As an example. Figures 3.7 and 3.8 display direct comparisons between the ground state experimental and DFT B3-LYP/6-31G calculated Raman spectra for DMABN and its ring deuterated isotopmer DMABN-d4. ° The experimental spectra are normal Raman spectra recorded in solid phase with 532nm excitation. For the calculated spectra, a Lorentzian function with a fixed band width of —10 cm was used to produce the vibrational band and the computed frequencies were scaled by a factor of 0.9614. 

As both F and G are partitioned by the use of symmetry coordinates, the secular determinant is factored accordingly. The problem of calculating the vibrational frequencies is thus divided into two parts solution of a linear equation for the single frequency of species B2 and of a quadratic equation for the pair of frequencies of species Aj. 

Vibrational frequencies of hexatriene and octatetraene have been reported by several authors21,24-26,36. The increase in the size of these molecules with respect to butadiene limits the use of highly accurate levels of calculation, so that a good choice of scaling factors is necessary to obtain useful results. Kofraneck and coworkers21 have shown that employing scale factors determined from vibrational data for trans structures alone does not give a balanced description of cis and trans structures. 

Table 2. Scale factors for ab initio model vibrational frequencies adapted from (Scott and Radom 1996). Please note that these scale factors are determined by comparing model and measured frequencies on a set gas-phase molecules dominated by molecules containing low atomic-number elements (H-Cl). These scale factors may not be appropriate for dissolved species and molecules containing heavier elements, and it is always a good idea to directly compare calculated and measured frequencies for each molecule studied. The root-mean-squared (rms) deviation of scaled model frequencies relative to measured frequencies is also shown, giving an indication of how reliable each scale factor is.

S, Cl and Si-isotope fractionations for gas-phase molecules and aqueous moleculelike complexes (using the gas-phase approximation) are calculated using semi-empirical quantum-mechanical force-field vibrational modeling. Model vibrational frequencies are not normalized to measured frequencies, so calculated fractionation factors are somewhat different from fractionations calculated using normalized or spectroscopically determined frequencies. There is no table of results in the original pubhcation. 

Similar methods have been used to integrate thermodynamic properties of harmonic lattice vibrations over the spectral density of lattice vibration frequencies.21,34 Very accurate error bounds are obtained for properties like the heat capacity,34 using just the moments of the lattice vibrational frequency spectrum.35 These moments are known35 in terms of the force constants and masses and lattice type, so that one need not actually solve the lattice equations of motion to obtain thermodynamic properties of the lattice. In this way, one can avoid the usual stochastic method36 in lattice dynamics, which solves a random sample of the (factored) secular determinants for the lattice vibration frequencies. Figure 3 gives a typical set of error bounds to the heat capacity of a lattice, derived from moments of the spectrum of lattice vibrations.34 Useful error bounds are obtained... 

The intensities of the infrared absorptions and of the inelastic scattered light (Raman) are determined by such electrical factors as dipole moments and polarizabilities. At the time of the pioneering studies on the infrared spectra of carbohydrates by the Birmingham school,7"11 calculations of the vibrational frequencies had been performed only for simple molecules of fewer than ten atoms.27,34,35 However, many tables of group frequencies, based on empirical or semi-empirical correlations between spectra and molecular structure, are available.32,34"37... 

In this formula, vibration frequency in a separate potential well and p is the momentum within the region where classic motion is forbidden. The physical meaning of this formula is simple. The splitting energy is determined chiefly by the coordinate region between the potential wells and, consequently, is proportional to exp( - j p dx). The magnitude of the preexponential factor can be further determined (with an accuracy of up to n) on the basis of the dimensional consideration. 

Figure 7.12 compares the measured and the theoretical absorption spectra for CH30N0(S i), the latter being obtained in a three-dimensional wavepacket calculation (Untch, Weide, and Schinke 1991a). The energy spacing of the main progression reflects the vibrational frequency of NO in the Si complex. The ratio of the peak intensities is mainly determined by the one-dimensional Franck-Condon factors... 

In accord with an approach originally outlined by Jortner and coworkers,41 42 the influence of changing AG° upon the 180 KIE has been modeled using a saddle point approximation.43 At this stage, the experimental variations in 180 KIEs for reactions of O2 and O2" are yet to be determined. The vibronic model of Hammes-Schiffer, which has been used to model proton-coupled electron transfer in accord with a Bom-Oppenheimer separation of timescales, may also be applicable here.44 The objective is to account for the change in 0—0 vibrational frequency together with potential contributions from overlap of vibrationally excited states. The overlap factors involving these states are expected to become more important as AG° deviates from 0 kcal mol 1,39... 

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