Integrated absorption intensities definition

Section BT1.2 provides a brief summary of experimental methods and instmmentation, including definitions of some of the standard measured spectroscopic quantities. Section BT1.3 reviews some of the theory of spectroscopic transitions, especially the relationships between transition moments calculated from wavefiinctions and integrated absorption intensities or radiative rate constants. Because units can be so confusing, numerical factors with their units are included in some of the equations to make them easier to use. Vibrational effects, die Franck-Condon principle and selection mles are also discussed briefly. In the final section, BT1.4. a few applications are mentioned to particular aspects of electronic spectroscopy. 

Analysis of Defined Fractions. Quantitative infrared analysis was used for those fractional groups that have definitive bands average absorptivities were estimated using model compounds (12, 16, 17). Table I lists the infrared bands and the apparent integrated absorption intensities (B) used. Quantitative IR spectra were measured in methylene chloride with 0.05 cm sodium chloride cells, using a Perkin-Elmer 521 infrared spectrophotometer. Peak area was measured by planimetry. Molecular weights were determined by vapor-pressure osmometry in benzene. 

The spectral overlap integral J can be expressed in terms of either wavenumbers or wavelengths (Equation 2.36). The area covered by the emission spectrum of D is normalized by definition and the quantities / and lx are the normalized spectral radiant intensities of the donor D expressed in wavenumbers and wavelengths, respectively. Note that the spectral overlap integrals J defined here differ from those relevant for radiative energy transfer (Equation 2.33). Only the spectral distributions of the emission by D /,P and, are normalized, whereas the transition moment for excitation of A enters explicitly by way of the molar absorption coefficient sA. The integrals J" and Jx are equal, because the emission spectrum of D is normalized to unit area and the absorption coefficients sA are equal on both scales. 

The 909 cm band is fairly isolated in frequency from the other absorptions and would normally be integrated easily. However, as compensation by the reference beam becomes poorer from condensation on the cryostat, the absorption at 926 cm" fluctuates and imparts large errors to the integration. Therefore, the best monitor that is available is the peak height (Figure 29). Quenched and annealed samples show definite changes in their slopes at Tg(L). The yi and Tg(U) transitions correspond to the temperatures where changes of slope are noticed for the slow-crystallized sample s intensity. 

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