By Ilya Prigogine
A part of a chain dedicated to supporting the reader receive basic information regarding a wide selection of themes in chemical physics. Its objective is to provide accomplished 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
The potential energy of the system solute/solvent is lowered by the resulting electrostatic interaction energy. In the simplified MSI model, the polarization of the surrounding solvent cage is approximated as the sum of incremental interactions of the actual charge distribution of the molecule with the solvent. The charge distribution is calculated using a quantum-chemical method, which is independent of the Onsager factor l / a 3 appearing in Eq. 20). Solutes ~ ~ ’ ~ ~of different size and shape can be compared directly, as will be described in the next section.
10 \ \ ijn-500 0 Fig. 23. Stationary spectra SST(Y)calculated [Eq. 40)] with A t = 5000 cm ' for different values of the ratio T , / T ~and assuming k , = l / ~ S(Y) ~ : given by Eq. "" iI ij,lOOOO -, 43 PHOTOPHYSICS OF INTERNAL TWISTING difference observed between the widths of the instantaneous and stationary emissions of the TICT state was of the order of 10%: the spectra have generally an equivalent AGO value at about 5000 cm-’ except at very low temperature in alcohols where ACo is smaller but where the relaxation is very slow ( T J T ~ 1).
98 48 E. LIPPERT ET AL. the dialkylamino group possesses only one electron in its lone-pair But the observed linear relationship of the quantum yield ratio 4A/4Rwith added small concentrations of a polar solvent is not a proof for exciplex formation, as we just have seen for the Langmuir-adsorption-isotherm-typeexample. Instead, correlations with steric effects of quencher molecules (with shielded or unshielded lone pairs)98show that saturated tertiary amines (and possibly even ethers) can form specific interactions with the molecule in its TICT state.
Advances in Chemical Physics, Vol. 68 by Ilya Prigogine