Quantum yield temperature dependence

Some aromatic carbonyl compounds have a low-lying n-n excited state and thus have a reasonable quantum yield (e.g. 0.12 for fluorenone in ethanol at 77 K and 0.01 at room temperature). However, if an n-n state lies only slightly higher in energy, the fluorescence quantum yield strongly depends on the polarity of the... 

Sun Y-P, Wang P and Hamilton N B 1993 Fluorescence spectra and quantum yields of Buckminsterfullerene (Cgg) in room-temperature solutions. No excitation wavelength dependence J. Am. Chem. Soc. 115 6378-81... 

The LIF technique is extremely versatile. The determination of absolute intermediate species concentrations, however, needs either an independent calibration or knowledge of the fluorescence quantum yield, i.e., the ratio of radiative events (detectable fluorescence light) over the sum of all decay processes from the excited quantum state—including predissociation, col-lisional quenching, and energy transfer. This fraction may be quite small (some tenths of a percent, e.g., for the detection of the OH radical in a flame at ambient pressure) and will depend on the local flame composition, pressure, and temperature as well as on the excited electronic state and ro-vibronic level. Short-pulse techniques with picosecond lasers enable direct determination of the quantum yield [14] and permit study of the relevant energy transfer processes [17-20]. 

The model [39] was developed using three assumptions the conformers are in thermodynamic equilibrium, the peak intensities of the T-shaped and linear features are proportional to the populations of the T-shaped and linear ground-state conformers, and the internal energy of the complexes is adequately represented by the monomer rotational temperature. By using these assumptions, the temperature dependence of the ratio of the intensities of the features were equated to the ratio of the quantum mechanical partition functions for the T-shaped and linear conformers (Eq. (7) of Ref. [39]). The ratio of the He l Cl T-shaped linear intensity ratios were observed to decay single exponentially. Fits of the decays yielded an approximate ground-state binding... 

The validity of the above conclusions rests on the reliability of theoretical predictions on excited state barriers as low as 1-2 kcal mol . Of course, this required as accurate an experimental check as possible with reference to both the solvent viscosity effects, completely disregarded by theory, and the dielectric solvent effects. As for the photoisomerization dynamics, the needed information was derived from measurements of fluorescence lifetimes (x) and quantum yields (dielectric constant, where extensive formation of ion pairs may occur [60], the observed photophysical properties are confidently referable to the unperturbed BMPC cation. Figure 6 shows the temperature dependence of the... 

By examining any correlation between excimer formation (as evidenced by characteristic excimer fluorescence) and dimerization quantum yield, one could perhaps determine whether dimerization is dependent upon prior excimer formation. Excimer fluorescence from anthracene solutions at room temperature is negligible although it has been observed in the solid state at low temperature.<75) Unfortunately, the data for substituted anthracenes allow no firm conclusions to be drawn. Some derivatives dimerize but do not exhibit excimer fluorescence. Others both dimerize and show excimer fluorescence. Still others show excimer fluorescence but do not dimerize and finally, some neither dimerize nor show excimer fluorescence. Hopefully, further work will determine what role excimer formation plays in this photodimerization. 

The quantum yield for the formation of the cycloaddition product has been found to be temperature dependent, increasing by a factor of approximately three as the temperature is lowered from 65 ( = 0.24) to 5°C ( = 0.69). Photolysis of mixtures of the olefin and f/my-stilbene in the presence of sensitizers yielded no cycloaddition product (42) but rather only m-stilbene. This suggests that the cycloadduct is produced via a singlet reaction. This conclusion is supported by the fact that tetramethylethylene quenches fluorescence from the /rans-stilbene singlet. A plot of l/ (42) vs. 1/[TME] (TME = tetramethylethylene) is linear. The slope of this plot yields rate constants for cycloadduct formation which show a negative temperature dependence. To account for this fact, a reversibly formed exciplex leading to (42) was proposed in the following mechanism<82) ... 

All members of the family [Pt(NH3) Cl4-w]n-a photo-aquate (39). a s-[Pt(NH3)2Cl2] yields the product [Pt(NH3)2(H20)Cl]+ with a quantum yield 0.46 at 350 nm and 25 °C (40). The yield is dependent upon both wavelength and temperature. The trans isomer also photo-aquates but with a quantum yield of 0.01. There has been a report that with light below 200 nm photo-oxidation can take place generating polynuclear Pt(II)— Pt(IV) species (41). [Pt(NH3)3Cl]+ photolyses to give ammonia and chloride aquation (42). [Pt(IV)Cle]2 photo-aquates. 

Molecular rotors are fluorophores characteristic for having a fluorescent quantum yield that strongly depends on the viscosity of the solvent [50], This property relies on the ability to resume a twisted conformation in the excited state (twisted intramolecular charge transfer or TICT state) that has a lower energy than the planar conformation. The de-excitation from the twisted conformation happens via a non-radiative pathway. Since the formation of the TICT state is favored in viscous solvents or at low temperature, the probability of fluorescence emission is reduced under those conditions [51]. Molecular rotors have been used as viscosity and flow sensors for biological applications [52], Modifications on their structure have introduced new reactivity that might increase the diversity of their use in the future [53] (see Fig. 6.7). 

The photosensitized results are from I.B.C. Matheson and J. Lee 118h It is seen that the quantum yields in photosensitized oxidation depend on the concentrations of luminol and base, and on temperature. At higher temperature (50°) and low luminol concentrations, the quantum yields reached those of hemin-catalyzed hydrogen peroxide oxidation of luminol in aqueous-alkaline solution. Primary products of the photosensitized oxidation are singlet oxygen (1Ag02) or a photoperoxide derived from methylene blue, but neither of these is directly responsible for the luminol chemiluminescence. 

The quantum yield of the selected azoalkanes photodecomposition are given in Table 3.18. The extinction coefficient s depends on the wavelength of light, and for AIBN in benzene solution (room temperature) has the values as given below [205] ... 

A modified SILAR system has been used to grow CdSe in CdS/CdSe core shell semiconductor nanocrystals.12 A cadmium precursor solution, with CdO dissolved with oleic acid in octadecane, was injected onto the substrate, and the Se solution (Se powder dissolved with tributylphosphine in octadecane) was similarly injected. The temperature of the reaction solution was 185 °C. A CdS outer layer in the CdS/CdSe/CdS colloidal quantum wells was deposited by alternating injections of cadmium and sulfur both in octadecane solutions at 230-240 °C. These structures showed high PL quantum yields (20-40%), relatively narrow emission bands, and tunable emission colors from about 520 to 650 nm depending on the number of CdSe monolayers. 

Due to the separation between excitation and emission in a fluorescence spectrometer, concentrations can be detected down to picomolar, with a wide linear range over up to five orders of magnitude. As a consequence of,e.g.,vibra-tional relaxation, the amount of energy which is released as fluorescence (quantum yield) is strongly dependent on solvent and temperature. 

The temperature dependence of luminescent metal complexes can be controlled by molecular design that affects the energy gap between the emitting state and the deactivating d-d or by altering the preexponential factor for thermal deactivation. The sometimes large temperature dependencies of lifetime and quantum yields for metal complexes also suggest their use as temperature sensors. 

Mislow and co-workers (258) and Hammond (259) have shown that optically active diaryl sulfoxides, which are configurationally stable in the dark at 200°C, lose their optical activity after 1 hr at room temperature on irradiation with ultraviolet light. Similarly, an easy conversion of the trans isomer of thianthrene-5,10-oxide 206a into the thermodynamically more stable cis isomer takes place upon irradiation in dioxane for 2 hr. However, the behavior of a-naphthylethyl p-tolyl sulfoxide under comparable irradiation conditions is different, namely, it is completely decomposed after 4 min. These differences are not surprising because the photochemical racemization of diaryl sulfoxides occurs by way of the pyramidal inversion mechanism whereas decomposition of the latter sulfoxide occurs via a radical mechanism with the cleavage of the sulfur-carbon bond. It is interesting to note that photoracemization may be a zero-order process in which the rate depends only on the intensity of the radiation and on the quantum yield. 

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