Relaxation radiative

Oq, and, if die trap cycle field couples to die 0 long-range molecular state [57], die second Condon point occurs at 60 <3q. Survival against radiative relaxation improves greatly because die optical coupling occurs at much shorter... 

As mentioned in the introductory part of this section, quantum dots exhibit quite complex non-radiative relaxation dynamics. The non-radiative decay is not reproduced by a single exponential function, in contrast to triplet states of fluorescent organic molecules that exhibit monophasic exponential decay. In order to quantitatively analyze fluorescence correlation signals of quantum dots including such complex non-radiative decay, we adopted a fluorescence autocorrelation function including the decay component of a stretched exponential as represented by Eq. (8.11). 

Here, a is a stretched factor, and Xdark is the characteristic time of the non-radiative relaxation. 

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. 

Figure 7.5 Schematic presentation of photoactivation and relaxation processes in a CdSe quantum dot aggregate (a) surface-passivation of photoexcited quantum dots by solvent molecules or dissolved oxygen, (b) thermal activation followed by the formation ofa stabilized state, (c) the formation of deep-trap states, (d) non-radiative relaxation of deep-...

Studies of the energetics and dynamics of Cu2 and Ag2 in rare gas solids have also been completed (31,34). The absorption and fluorescence spectra are similarly indicative of strong guest-host interactions in the low lying states of Cu2 and Ag2 Rather than presenting the spectroscopic and photolytic details, a summary of the observed radiative relaxation processes of visible and uv excited Cu2 and Ag2 in rare gas solids is shown below ... 

It should be noted that no emission from the zwitterionic form of the proton-transferred tautomer was observed from any of the benzotriazoles studied in the present work. This implies that non-radiative relaxation processes from the excited state of this species are very efficient in all of the solvent and polymer environments studied. Thus no information is available on the effect of the medium polarity on the room-temperature photophysics of the zwitterionic form using fluorescence techniques. 

Turning to the fully quantum mechanical approach, we find that the lowest order rate theory for general non-radiative relaxation processes also provides a factorized rate expression ... 

Figure 5. Rate-energy curves for benzene ion dissociation. Circles are TRPD points (corrected for IR-radiative relaxation) from Ref. 24 squares are REMPI points from Ref. 10. The two points with ( ) symbols are TRPD points uncorrected for radiative relaxation. The curves are from variational RRKM, with Eq = 3.88 eV, and simple RRKM, with Eo = 3.81 eV.

If the electron enters a Rydberg orbital on one of the protonated amine sites, in addition to undergoing a cascade of radiative or non-radiative relaxation steps to lower-energy Rydberg states, it can subsequently undergo intra-peptide electron transfer to either an SS cr or an OCN n orbital after which disulfide or N-Cr, bond cleavage can occur [3r,3u-3w]. 

Trivalent samarium activated minerals usually display an intense luminescence spectrum with a distinct hne structure in the red-orange part of the spectrum. The radiating term 65/2 is separated from the nearest lower level 11/2 by an energy interval of 7,500 cm This distance is too large compared to the energy of phonons capable to accomplish an effective non-radiative relaxation of excited levels and these processes do not significantly affect the nature of their spectra in minerals. Thus all detected lines of the Sm " luminescence take place from one excited level and usually are characterized by a long decay time. 

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