Download PDF by Leszczynski J. (ed.): Computational Chemistry.. Reviews of Current Trends

By Leszczynski J. (ed.)

ISBN-10: 9812387021

ISBN-13: 9789812387028

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228 In the excited state, the initially uncomplexed solute monomer can I n-hexaneln-butyronitrile IP) -u2-' 0 I I I 300 350 LOO I Xlnm L50 n-hexaneln - butyroni t rile - - - - . . 350 1 LOO I 1 L50 Xlnm 500 I 550 Fig. 25. Quenching effect on the short-wavelength FB fluorescence band of two different TICT state-forming compounds by adding traces of a polar solvent P to a nonpolar solution. Successive spectra correspond to repeated addition of small amounts of n-butyronitrile to initially 50mL n-hexane solution, -5 X MIL.

Chan. 50 I /ns 5 100 " " 1 ' 288 150 " 10 ' I " " I 15 ' 20 Fig. 17. 91 ns]. 33 34 E. LIPPERT ET AL. At temperatures sufficiently below T,, the back reaction k,, is not fast enough to compete with k t and k ; , thus the entire decay curves can be thought of as representing equilibration without reaching it within the time given by the lifetime of the excited A* state. 17 shows an example measured with time-correlated single-photon counting. 86 Figure 2 . 1 7 ~shows that for compounds with a larger rotating amino moiety than in DMABN, this TICT formation rate in cooled n-butyl chloride is slow enough for the delayed appearance of the A* emission to be quite evident (Fig.

The effect on the spectra is shown in Fig. 10, where the very strong redshift of the A band with increasing solvent polarity is readily apparent. A simple way to quantify these redshifts and relate them to dipole moments of fluorescing species is the Lippert-Mataga equation 60-62.. N E C ~ :/BCI N [KJmole-’I 360 3LO 320 A-fluo (L13nml B-fluo 13L9nm) 60 LO 20 0 - reaction coordinate (twist. solvent reorientation,... 1 Fig. 9. Empirical energy diagram for DMABN in n-butyl chloride (energetics based on room-temperature fluorescence band maxima and on activation energies).

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Computational Chemistry.. Reviews of Current Trends by Leszczynski J. (ed.)


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