Emission spectra, excited state

The fast and non-delayed emission spectrum (Fig. 22 a) shows nearly the same structure as the time-integrated spectrum measured at T = 20 K. (Fig. 14) However, the satellites that result from state III (9 cm higher lying peaks of the doublet structure in the 20 K emission spectrum) do not occur in the fast spectrum. Obviously, at T = 1.3 K, an emission of state III is not observed. This is due to the very fast sir processes to the lower lying triplet substates II and I. (Compare also Sect. 4.2.9.) Thus, the fast spectrum represents the non-thermalized emission spectrum of state II. The Boltzmann distribution does not apply immediately after the excitation pulse, since the thermal equilibration is relatively slow. (For details see Refs. [22,24].) This state II emission spectrum is assigned... 

The interpretation of emission spectra is somewhat different but similar to that of absorption spectra. The intensity observed m a typical emission spectrum is a complicated fiinction of the excitation conditions which detennine the number of excited states produced, quenching processes which compete with emission, and the efficiency of the detection system. The quantities of theoretical interest which replace the integrated intensity of absorption spectroscopy are the rate constant for spontaneous emission and the related excited-state lifetime. 

By obtaining values for B in various vibrational states within the ground electronic state (usually from an emission spectrum) or an excited electronic state (usually from an absorption spectrum) the vibration-rotation interaction constant a and, more importantly, B may be obtained, from Equation (7.92), for that electronic state. From B the value of for that state easily follows. 

The resulting PL intensity depends on the absorption of the incident light and the mechanism of coupling between the initial excited states and the relaxed excited states that take part in emission. The spectrum is similar to an absorption spectrum and is useful because it includes higher excited levels that normally do not appear in the thermalized PL emission spectra. Some transitions are apparent in PLE spectra from thin layers that would only be seen in absorption data if the sample thickness were orders of magnitude greater. 

It is possible that Q is an excited state of Q if so, we will assume that its emission spectrum does not contribute to the fluorescence intensity at Vcnr Q is called a quencher, because in its presence the fluorescence intensity of solute A is reduced. 

The molecules of Nj so formed are in an excited state (B n ) and give rise to the emission of the first positive band system of the spectrum of molecular N2 in returning to the ground state... 

The electroluminescence spectra of the single-layer devices are depicted in Figure 16-40. For all these OPV5s, EL spectra coincided with the solid-state photoluminescence spectra, indicating that the same excited states are involved in both PL and EL. The broad luminescence spectrum for Ooct-OPV5-CN" is attributed to excimer emission (Section 16.3.1.4). 

Since an atom of a given element gives rise to a definite, characteristic line spectrum, it follows that there are different excitation states associated with different elements. The consequent emission spectra involve not only transitions from excited states to the ground state, e.g. E3 to E0, E2 to E0 (indicated by the full lines in Fig. 21.2), but also transisions such as E3 to E2, E3 to 1( etc. (indicated by the broken lines). Thus it follows that the emission spectrum of a given element may be quite complex. In theory it is also possible for absorption of radiation by already excited states to occur, e.g. E, to 2, E2 to E3, etc., but in practice the ratio of excited to ground state atoms is extremely small,... 

The fluorescence spectrum of dibenz[7>,/]oxepin shows that this molecule adopts a planar structure in the excited state whereas the ground state has bent geometry as expected.19 The emission spectrum is similar to that of anthracene. 

The Humphreys series is set of spectral lines in the emission spectrum of atomic hydrogen that ends in the fifth excited state. 

Theory. If two or more fluorophores with different emission lifetimes contribute to the same broad, unresolved emission spectrum, their separate emission spectra often can be resolved by the technique of phase-resolved fluorometry. In this method the excitation light is modulated sinusoidally, usually in the radio-frequency range, and the emission is analyzed with a phase sensitive detector. The emission appears as a sinusoidally modulated signal, shifted in phase from the excitation modulation and partially demodulated by an amount dependent on the lifetime of the fluorophore excited state (5, Chapter 4). The detector phase can be adjusted to be exactly out-of-phase with the emission from any one fluorophore, so that the contribution to the total spectrum from that fluorophore is suppressed. For a sample with two fluorophores, suppressing the emission from one fluorophore leaves a spectrum caused only by the other, which then can be directly recorded. With more than two flurophores the problem is more complicated but a number of techniques for deconvoluting the complex emission curve have been developed making use of several modulation frequencies and measurement phase angles (79). 

The divalent rare-earth ion Eu has the 4f electronic configuration at the ground states and the 4f 5d electronic configuration at the excited states. The broadband absorption and luminescence of Eu are due to 4f - 4 f 5d transitions. The emission of Eu is very strongly dependent on the host lattice. It can vary from the ultraviolet to the red region of the electromagnetic spectrum. Furthermore, the 4f-5d transition of Eu decays relatively fast, less than a few microseconds [33]. 

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