Linewidth, homogeneous

A result of tlie relaxation processes is a shortened lifetime of the spin states giving rise to a broadening of the EPR line, which for most magnetic resonance lines dominated by homogeneous linewidth can be written as... 

As the spins precess in the equatorial plane, they also undergo random relaxation processes that disturb their movement and prevent them from coming together fiilly realigned. The longer the time i between the pulses the more spins lose coherence and consequently the weaker the echo. The decay rate of the two-pulse echo amplitude is described by the phase memory time, which is the time span during which a spin can remember its position in the dephased pattern after the first MW pulse. Tyy is related to the homogeneous linewidth of the individual spin packets and is usually only a few microseconds, even at low temperatures. 

Therefore, the absorjDtion line is massively inlromogeneously broadened at low temperature. An inliomogeneous lineshape can be used to detennine the static or quasistatic frequency spread of oscillators due to a distribution of environments, but it provides no dynamical infonnation whatsoever [94, 95]. As T is increased to 300 K, the absorjDtion linewidth decreases and increases. At 300 K, the lineshape is nearly homogeneously broadened and dominated by vibrational dephasing, because fast dephasing wipes out effects of inliomogeneous environments, a well known phenomenon tenned motional narrowing [951. 

The homogeneous linewidth can be subdivided into distinctly different contributions,... 

Figure C3.5.9 shows all contributions to the homogeneous linewidth of W(CO)g in 2-MP. increases from...

Figure C3.5.9. Contributions to the homogeneous linewidth of a C=0 stretching transition of W(CO)g (Q 2000...

Unlike high-resolution NMR spectra of bulk solutions where NMR linewidths well below 1 Hz can be obtained routinely, NMR spectra of liquids permeating porous solids in most cases will not exhibit such a high spectral resolution. First of all, the interaction of liquid phase molecules with pore walls of the catalyst and rapid diffusion-driven intrapore transport will lead to a pronounced homogeneous broadening of the observed NMR lines. Smaller pore sizes and the presence of paramagnetic impurities in the solid material usually aggravate the situation and thus should be avoided. Another reason why NMR spectra of liquids in porous... 

FIGURE 4.2 Linewidth increase with temperature for an S = 1/2 system. The linewidth of a feature in the low-spin heme spectrum from cytochrome a in bovine heart cytochrome oxidase has been fit as a convolution of a constant component from inhomogeneous broadening and a temperature-dependent component from homogeneous broadening (Hagen 2006). (Reproduced by permission of The Royal Society of Chemistry.)... 

The last mentioned dynamical capability of lasers is in its infancy. It is possible in principle to make optical measurements which are analogous to coherent NMR measurements, and thereby to observe homogeneous linewidths in inhomogeneously broadened systems, to measure optical or vibrational Ti and T2 relaxation times directly, and to observe quantum recurrences. 

The single-mode laser naturally gives less output power than a multimode laser with the same active volume since its induced emission is concentrated into a smaller frequency range. This loss in intensity, however, is much less than one would expect from the ratio of linewidths or from the reduction in oscillating mode number 3i. 32,41) jbis is due to the fact, that not only atoms with the exact transition frequency can contribute to the induced emission, but also those inside the homogeneous linewidth which is determined by collision processes in the case of gas lasers or by crystal line broadening in solid lasers... 

This is a Gauss profile with a lorentzian hole, the width of which is determined by the homogeneous linewidth parameters 7ab> T with 7ab " rb depending on the lifetimes 7a, Tb of... 

The inability to "burn" a narrow hole in the polyethylene spectrum is an indication that the "natural homogeneous linewidth"... 

On the other hand, Schaefer ( ) has shown from selective saturation experiments of amorphous cis polyisoprene, crystalline trans polyisoprene, as well as carbon black filled cis polyisoprene, that the resonant lines are homogeneous. The linewidths in these cases are thus not caused by inhomogeneous broadening resulting from equivalent nuclei being subject to differing local magnetic fields. The results for these systems are thus contrary in part to what has been found here. 

FIGURE 5.5 (a) Components of the CARS signal. The last three terms in Equation 5.1 are plotted versus detuning A = C0p-co -O. O is the center frequency of a homogeneously broadened Raman line with linewidth F. The curves are calculated with an assumption that2 R = 1.2 = 0)- (b) Schematic of the FM CARS process. Solid curve, sum of the contribu-... 

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