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Rotational strength decrease

Fig. 7.5). When the molecules are far apart, the opposite rotational strengths of the two overlapping bands cancel. Figure 9.8 illustrates this point. In the example shown, the net CD increases as R2 is raised from 7 to 10 A (Fig. 9.8A), but then decreases at larger distances (Fig. 9.8B). Fig. 7.5). When the molecules are far apart, the opposite rotational strengths of the two overlapping bands cancel. Figure 9.8 illustrates this point. In the example shown, the net CD increases as R2 is raised from 7 to 10 A (Fig. 9.8A), but then decreases at larger distances (Fig. 9.8B).
At higher pressures only Raman spectroscopy data are available. Because the rotational structure is smoothed, either quantum theory or classical theory may be used. At a mixture pressure above 10 atm the spectra of CO and N2 obtained in [230] were well described classically (Fig. 5.11). For the lowest densities (10-15 amagat) the band contours have a characteristic asymmetric shape. The asymmetry disappears at higher pressures when the contour is sufficiently narrowed. The decrease of width with 1/tj measured in [230] by NMR is closer to the strong collision model in the case of CO and to the weak collision model in the case of N2. This conclusion was confirmed in [215] by presenting the results in universal coordinates of Fig. 5.12. It is also seen that both systems are still far away from the fast modulation (perturbation theory) limit where the upper and lower borders established by alternative models merge into a universal curve independent of collision strength. [Pg.182]


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Decrease

Decreasing

Rotational strength

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