Atomic height data

We start with the reaction of abstraction of a hydrogen atom by a CH3 radical from molecules of different matrices (see, e.g., Le Roy et al. [1980], Pacey [1979]). These systems were the first to display the need to go beyond the one-dimensional consideration. The experimental data are presented in table 2 together with the barrier heights and widths calculated so as to fit the theoretical dependence (2.1) with a symmetric gaussian barrier. 

Fig. 55. The potential of hindered rotation of the CH3 group in nitromethane (CH3NO2) crystal, (a) calculated from INS data, Vi = 0.586 kcal/mol, V = 0.356 kcal/mol, S = 30°, and (b) calculated with the atom-atom potential method [Cavagnat and Pesquer 1986]. The barrier height is 0.768 kcal/mol.

Fortunately, isotopic abundances as well as isotopic masses can be determined by mass spectrometry. The situation with chlorine, which has two stable isotopes, 0-35 and 0-37, is shown in Figure 3.2. The atomic masses of the two isotopes are determined in the usual way. The relative abundances of these isotopes are proportional to the heights of the recorder peaks or, more accurately, to the areas under these peaks. For chlorine, the data obtained from the mass spectrometer are... 

Calculations. The atoms of incorporated lsO is calculated from mass spectral data. When the ratio of the peak heights at mass-to-charge ratio (m/e) 44, 46 and 48 for CO2 is X-.Y-.Z, assuming that the height of each peak is strictly proportional to the number of CO2 molecules, the atom fraction of l80 in CO2, C, is given by ... 

The X-N technique is sensitive to systematic errors in either data set. As discussed in chapter 4, thermal parameters from X-ray and neutron diffraction frequently differ by more than can be accounted for by inadequacies in the X-ray scattering model. In particular, in room-temperature studies of molecular crystals, differences in thermal diffuse scattering can lead to artificial discrepancies between the X-ray and neutron temperature parameters. Since the neutron parameters tend to be systematically lower, lack of correction for the effect leads to sharper atoms being subtracted, and therefore to larger holes at the atoms, but increases in peak height elsewhere in the X-N deformation maps (Scheringer et al. 1978). 

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