By Ilya Prigogine
A part of a chain dedicated to supporting the reader receive basic information regarding a large choice of themes in chemical physics. Its objective is to offer accomplished analyses of topics of curiosity and to motivate the expression of person issues of view.
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Additional info for Advances in Chemical Physics, Vol. 68
It is possible to show that the following quantities remain invariant to this tran~formation'~: 56 E. LIPPERT ET AL. It is clear that, for example, the interpretation of the quantity KhLB depends on the choice of orbitals. 2. Energies and Wavefunctions of Biradicaloids If the real orthogonal orbitals ZB and 93 interact, yd3 ZO, or have different energies, S, ZO, or are both independent on the choice of orbitals, we refer to the system as a biradicaloid. 13) are IS;)=C. - 1~ZB2-932)+c;,+'~ZB2+932)+c;,"1~ZB93), i=0,1,2.
32) = k,, Around and above T,, the decay of the B band becomes biexponential, because the prefactors (x - A’) and (A, - x) in Eq. 28) become comparable in magnitude. The fast initial decay corresponds to the equilibration part, and the slower second component corresponds to the decay of the equilibrated system. Of course, for this later time period, the equilibrated system behaves as a single kinetic unit (high-temperature region: k,, B kf” + k: and k,, P k; + k $ ) , and B and A bands have identical decay times given by Eq.
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). In the “smallbarrier case,” E , is to be viewed as a “dynamical” activation energy resulting from solvent viscosity.