Phonon broadening

Wlrile tire Bms fonnula can be used to locate tire spectral position of tire excitonic state, tliere is no equivalent a priori description of the spectral widtli of tliis state. These bandwidtlis have been attributed to a combination of effects, including inlromogeneous broadening arising from size dispersion, optical dephasing from exciton-surface and exciton-phonon scattering, and fast lifetimes resulting from surface localization 1167, 168, 170, 1711. Due to tire complex nature of tliese line shapes, tliere have been few quantitative calculations of absorjDtion spectra. This situation is in contrast witli tliat of metal nanoparticles, where a more quantitative level of prediction is possible. 

For condensed species, additional broadening mechanisms from local field inhomogeneities come into play. Short-range intermolecular interactions, including solute-solvent effects in solutions, and matrix, lattice, and phonon effects in soHds, can broaden molecular transitions significantly. 

The corresponding level broadening equals half. In fact is the diagonal kinetic coefficient characterizing the rate of phonon-assisted escape from the ground state [Ambegaokar 1987]. In harmonic approximation for the well the only nonzero matrix element is that with /= 1,K0 Q /> = <5o, where is the zero-point spread of the harmonic oscillator. For an anharmonic potential, other matrix elements contribute to (2.52). 

The lack of a well-defined specular direction for polycrystalline metal samples decreases the signal levels by 10 —10, and restricts the symmetry information on adsorbates, but many studies using these substrates have proven useful for identifying adsorbates. Charging, beam broadening, and the high probability for excitation of phonon modes of the substrate relative to modes of the adsorbate make it more difficult to carry out adsorption studies on nonmetallic materials. But, this has been done previously for a number of metal oxides and compounds, and also semicon-... 

According to the quantum transition state theory [108], and ignoring damping, at a temperature T h(S) /Inks — a/ i )To/2n, the wall motion will typically be classically activated. This temperature lies within the plateau in thermal conductivity [19]. This estimate will be lowered if damping, which becomes considerable also at these temperatures, is included in the treatment. Indeed, as shown later in this section, interaction with phonons results in the usual phenomena of frequency shift and level broadening in an internal resonance. Also, activated motion necessarily implies that the system is multilevel. While a complete characterization of all the states does not seem realistic at present, we can extract at least the spectrum of their important subset, namely, those that correspond to the vibrational excitations of the mosaic, whose spectraFspatial density will turn out to be sufficiently high to account for the existence of the boson peak. 

Finally, we return to the specific heat. The effects of the phonon coupling on the ripplon spectrum can be taken into account in the same fashion as in the conductivity case. Here we replace the discrete summation in Eq. (38) by integration over the broadened resonances, as prescribed by Eq. (57). The bump, as shown in Fig. 15, is also predicted to be nonuniversal depending on Tg/oio-The predicted bump for Tg/(Od = 2 seems to match well the available data for... 

In addition to the photoluminescence red shifts, broadening of photoluminescence spectra and decrease in the photoluminescence quantum efficiency are reported with increasing temperature. The spectral broadening is due to scattering by coupling of excitons with acoustic and LO phonons [22]. The decrease in the photoluminescence quantum efficiency is due to non-radiative relaxation from the thermally activated state. The Stark effect also produces photoluminescence spectral shifts in CdSe quantum dots [23]. Large red shifts up to 75 meV are reported in the photoluminescence spectra of CdSe quantum dots under an applied electric field of 350 kVcm . Here, the applied electric field decreases or cancels a component in the excited state dipole that is parallel to the applied field the excited state dipole is contributed by the charge carriers present on the surface of the quantum dots. 

Table 4.1. Various processes contributing to the spectral line broadening for local vibrations. Frequencies of collectivized local vibrations QK (solid arrows) are supposed to exceed phonon frequencies oiRq (dashed arrows) Ok > max oncq. For an extremely narrow band of local vibrations, diagrams A and B respectively refer to relaxation and dephasing processes, whereas diagrams C account for the case realizable only at the nonzero band width for local vibrations.

Brownian motion, other mechanisms, as for instance, a decay of a local vibration into substrate phonons (see Chapter 4) or inhomogeneous broadening caused by static shifts of oscillator frequencies in random electric fields of a disordered dipole environment. A temperature dependence of a broadening arising from these additional effects should be considerably weaker than the exponential dependence in Eq. (A2.26) or (A2.4). The total broadening is therefore expressible as... 

Phonon broadening, 34 247,253 Phosgene, catalytic synthesis, 28 270-273 Phosphanes aliphatic, 42 493 hydroxyalkyl-substituted, 42 482 quaternary ammonium, 42 492 sugar derivatives, 42 482-483 sulfonated, 42 476-478 Phosphanorbomadienes... 

A substantial linewidth broadening of the adlayer modes in the whole region near T where they overlap the bulk phonon bands of the substrate the excited adlayer modes may decay by emitting phonons into the substrate they become leaky modes. These anomalies were expected to extend up to trilayers even if more pronounced for bi- and in particular for monolayers. 

Experimental data of Gibson and Sibener appears to confirm qualitatively these predictions at least for monolayers. The phonon linewidths were broadened around T up to half of the Brillouin zone. The hybridization splitting could not be resolved, but an increase of the inelastic transition probability centered around the crossing with the Rayleigh wave and extending up to 3/4 of the zone has been observed and attributed to a resonance between the adatom and substrate modes. 

Fig, 26. Experimental dispersion curve of the Kr monolayer and measured line width broadening As of the Kr creation phonon peaks. The solid line in the dispersion plot is the clean Pt(lll) Rayleigh phonon dispersion curve and the dashed line the longitudinal phonon bulk band edge of the Pt(l 11) substrate, both in the r Mn azimuth which is coincident with the r Kk, azimuth. 

Brillouin scattering of laser light in liquids has been studied by several authors. Shapiro etal. 233) measured hypersonic velocities in various liquids and obtained a Brillouin linewidth of 0.011 cm" in methylene chloride but of less than 0.002 cm in benzene, carbon disulfide and chloroform. The broadening of the Brillouin components arises from damping of thermal phonons and is closely connected with the viscosity coefficient of the medium. From the measured linewidths, the lifetimes of the phonons responsible for Brillouin scattering at 89 45 were calculated to be 4.8 x 10 sec for methylene chloride and 7.6 x 10 sec for toluene. 

There are a large number of cases where the spectra of luminescence centers remain broad up to helium temperatures. In certain cases, this is explained by a strong electron-phonon interaction, but more often the inhomogeneous broadening, connected with several types of the same center presence, causes this. In such cases it is possible to simplify the spectrum by selective excitation of specific centers. 

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