Advances in Chemical Physics, Vol. 68 by Ilya Prigogine

By Ilya Prigogine

A part of a sequence dedicated to aiding the reader receive common information regarding a large choice of subject matters in chemical physics. Its target is to give entire analyses of topics of curiosity and to motivate the expression of person issues of view.

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In the case that two orbitals d and 9 interact weakly, the two-electron states are not adequately described by the single configuration because all three singlet configurations (d’, d B ) must be treated equally (3 x 3 CI). The triplet is of course represented by a single configuration. If two orbitals are degenerated the “broken” system is denoted as perfect biradical; if they differ in energy, the system is referred to as a biradicaloid. Since we are primarily interested in dative bonds, d 2and 9’differ in energy and we will use the convention that 9*is lower in energy than d’.

20). Solutes ~ ~ ’ ~ ~of different size and shape can be compared directly, as will be described in the next section. 2. The TICT Excited-State Dipole Moment Consider a cage of solvent molecules with a thickness Ars around a solute molecule with the total surface S (Fig. 11). The thickness Ar, is of minor importance since it will not appear explicitly in our final results. The surface S will be divided rather arbitrarily in subsurfaces S, of subgroups i for each atom except hydrogen, that is, for C, 0, and N in our examples, which carry the fractional charge Q j of the subgroup i.

22). 12 n m l c h a n n d ) Fig. 21. 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.

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