Spectral envelope

The spectral frequency range covered by the central lobe of this sinc fiinction increases as the piilselength decreases. For a spectrum to be undistorted it should really be confined to the middle portion of this central lobe (figure B 1.12.2). There are a number of examples in the literature of solid-state NMR where the resonances are in fact broader than the central lobe so that the spectrum reported is only effectively providing infonnation about the RF-irradiation envelope, not the shape of the signal from the sample itself... 

The quantum theory of spectral collapse presented in Chapter 4 aims at even lower gas densities where the Stark or Zeeman multiplets of atomic spectra as well as the rotational structure of all the branches of absorption or Raman spectra are well resolved. The evolution of basic ideas of line broadening and interference (spectral exchange) is reviewed. Adiabatic and non-adiabatic spectral broadening are described in the frame of binary non-Markovian theory and compared with the impact approximation. The conditions for spectral collapse and subsequent narrowing of the spectra are analysed for the simplest examples, which model typical situations in atomic and molecular spectroscopy. Special attention is paid to collapse of the isotropic Raman spectrum. Quantum theory, based on first principles, attempts to predict the. /-dependence of the widths of the rotational component as well as the envelope of the unresolved and then collapsed spectrum (Fig. 0.4). 

Figure 7 shows the latter, spectral envelope for different incident angles and illustrates the superblaze envelope obtained by simultaneously optimising both wavelength and incident angle. 

A delay error shifts the position of zero delay with respect to the overall intensity envelope, resulting in a substantial reduction of overall contrast. The contrast may vanish entirely if the zero delay position coincides with a minimum. Therefore, there is a relation between the allowable delay error max and the spectral bandwidth Aoj of the detected radiation if the amplitude error of the fringe modulation is to remain small, i. e., (5max = A /AA. 

The applicability of the ESE envelope modulation technique has been extended by two recent publications115,1161. Merks and de Beer1151 introduced a two-dimensional Fourier transform technique which is able to circumvent blind spots in the one-dimensional Fourier transformed display of ESE envelope modulation spectra, whereas van Ormondt and Nederveen1161 could enhance the resolution of ESE spectroscopy by applying the maximum entropy method for the spectral analysis of the time domain data. 

Cable et al. also noted two distinct bands in the region 1000—950 cm, in which resides the absorption envelope for the symmetric C—O—C stretching vibration. This spectral feature was earlier observed by Heitner-Wirguin" as well as Lowry and Mauritz.Heitner-Wirguin noted a small shift in this band when the Na+ counterion is replaced by transition metal counterions. The spectra of Lowry and Mauritz for dry Li+, Na+, K ", and Rb" forms... 

In the case of NOS 12, different kinetics were observed at 436 nm. In cyclohexane, there was a rapid rise, with a lifetime of 6.6 psec followed by a decay with a 100-psec lifetime. In 1-butanol, there was a rapid rise (lifetime=4.3 psec), a decay (43-psec lifetime), and a second longer decay within a 1.4-nsec lifetime. These findings were confirmed by picosecond time-resolved resonance Raman spectroscopy. In these Raman studies in cyclohexane, a single rate constant was observed, whereas in 1-butanol, three spectral components grew with different time constants. The data were said to be consistent with the photo-formation of two or three isomers trans about the central methine bond however, other transient species could be responsible for the observed kinetics because the absorption envelope obviously shifts and this would affect the resonance Raman bands. 

Table I. Reeulbs of spectral envelope deconvolution calcuUttions carried...

The term that depends on the third power of the frequency shift is known as third-order dispersion (TOD). When a TL pulse acquires a significant amount of TOD, the pulse envelope is distorted and a series of sub-pulses is produced, as shown in Figure 8.1. Unlike a pulse with SOD, a pulse with TOD leads to two-photon excitation with the same efficiency as a TL pulse but only for a particular two-photon frequency. At other frequencies, the amount of excitation is suppressed. The control over TOD would allow for preferential excitation in different spectral regions, while its correction would lead to efficient two-photon excitation over the whole accessed spectral range. Unfortunately, measuring and correcting TOD is not a simple task. 

Black lamps A black lamp is a low-pressure mercury lamp whose envelope is covered with a phosphor such as strontium fluoroborate or barium disilicate. The type of phosphor determines the spectral distribution of the lamp output (Forbes et al., 1976). Figure 16.4 shows a typical spectral distribution for A < 500 nm from a black lamp as well as the solar... 

Sunlamps A sunlamp is similar to a black lamp, except that a different type of phosphor is used and the lamp envelope transmits UV. Figure 16.5 shows a typical spectral distribution from a commercial sunlamp. The wavelength corresponding to maximum power is shifted to lower wavelengths (— 310 nm), compared to black lamps, and there is significant intensity down to 270 nm. However, the intensity decreases rapidly above 330 nm. The mercury lines can again be seen superimposed on the phosphor fluorescence. 

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