By Ilya Prigogine
A part of a sequence dedicated to aiding the reader receive normal information regarding a large choice of subject matters in chemical physics. Its objective is to give entire analyses of matters of curiosity and to inspire the expression of person issues of view.
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Additional info for Advances in Chemical Physics, Vol. 68
From Eq. 40) it is clear that the position of the stationary ~ )the deactivation spectrum is a function of <), A < , and the ratio ( T ~ / T of and relaxation rates. The broadening of the stationary emission with , with respect to the instant spectrum is maximum for T~ = T ~ increases A C , and gains in importance for small initial widths. This is illustrated in Fig. 23, representing the stationary emission calculated for two values of the width A;, at half-maximum of an instant distribution assumed to be of the form 1 Avo ...
DMABN/propanol at -80°C: experimental (- . ) and calculated (-) decay curves at different wavelengths. 89 E. LIPPERT ET AL. Fig. 22. 5 ns; +, t = 5 n ~ . 3). They lead to the conclusion that the wavenumber Cm(t) characterizing the position of the emission at time t is given by PHOTOPHYSICS OF INTERNAL TWISTING 41 where and v”m define, respectively, the position at times t = 0 (unrelaxed state) and t + m (relaxed state) and T~ is the spectral relaxation time constant related to the solvent relaxation time T , = ( E , / E & ~ , where and E,, are the optical and low-frequency dielectric constants and T,, is the dielectric relaxation time constant.
12 shows 10 Fig. 12. '~ 28 E. LIPPERT ET AL. an aromatic sulfone where the second fluorescence is strongly enhanced in polar solvents. 8,74Michler’s Ketone, which has a structure similar to the sulfone shown in Fig. 12, but with the SO, group exchanged for C=O, also shows TICT fluorescence identified by its solvatochromy which will be discussed in more detail in Section V. Fig. 13. ” 29 PHOTOPHYSICS OF INTERNAL TWISTING Dual fluorescences have also been discovered in biaromatic compounds without any substituent.