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The exact assignment of the bands is possible considering solvatochromic and electrochemical data obtained in different solvents and the orbital energy scheme of Model 3 described by Barlow et al, see ref 24 and the Supporting Information
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In order to calculate exactly such experimental parameters, some simulations of such absorption bands have been performed by using the TableCurve Software
-
In order to calculate exactly such experimental parameters, some simulations of such absorption bands have been performed by using the TableCurve Software.
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69
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34249098206
-
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For all the band shape analysis, an epsilon vs wavenumber [cm -1] representation of the absorption spectra has to be used, since in this way a linear relationship with the energy is obtained
-
-1] representation of the absorption spectra has to be used, since in this way a linear relationship with the energy is obtained.
-
-
-
-
80
-
-
34249105983
-
-
Asymmetry in the band shape of Class II systems mostly arises from additional contributions of transitions from low-lying vibrational levels. An exact band shape analysis affords a quantum mechanical treatment Franck-Condon analysis, which is ongoing work in our research group; see ref 38
-
Asymmetry in the band shape of Class II systems mostly arises from additional contributions of transitions from low-lying vibrational levels. An exact band shape analysis affords a quantum mechanical treatment (Franck-Condon analysis), which is ongoing work in our research group; see ref 38.
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34249072371
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0 is calculated to be 6.17 and 6.38 Å for compounds 1 and 2, respectively. The use of an effective spherical radius is a clear simplification in the case of the complex molecular geometries studied here.
-
0 is calculated to be 6.17 and 6.38 Å for compounds 1 and 2, respectively. The use of an effective spherical radius is a clear simplification in the case of the complex molecular geometries studied here.
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Usually the following values are used for such corrector parameter: δ, 0.0 for non-chlorinated aliphatic solvents, δ, 0.5 for polychlorinated aliphatic solvents, and δ, 1 for aromatic solvents
-
Usually the following values are used for such corrector parameter: δ = 0.0 for non-chlorinated aliphatic solvents, δ = 0.5 for polychlorinated aliphatic solvents, and δ = 1 for aromatic solvents.
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106
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Two solvents were discarded in the LSER treatments of dyads 1 and 2 given in Table S1, since they do not follow the general trends of other solvents, probably because of the presence of impurities; see ref 52
-
Two solvents were discarded in the LSER treatments of dyads 1 and 2 given in Table S1, since they do not follow the general trends of other solvents, probably because of the presence of impurities; see ref 52.
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113
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34249031062
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-
For the calculations, we have used α, β, and π* parameters from ref 45 since they were derived under the same conditions. Despite using parameters from different sources for the multiple regression analysis, very similar results have been obtained.
-
For the calculations, we have used α, β, and π* parameters from ref 45 since they were derived under the same conditions. Despite using parameters from different sources for the multiple regression analysis, very similar results have been obtained.
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114
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34249079885
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SYSTAT for Windows, Version 5; SYSTAT, Inc, Evanston, IL, 1992
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34249090886
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By performing a coefficient analysis of each independent variable, we saw that some of the solvents could be left out of the analysis. From the plotting of the experimental values versus the calculated values, we also found that there were some solvents that do not follow the regression model. After those solvents were eliminated, the resulting fits were much better. For the new fits, the linear regression model was valid, with a significance superior - F = 47, p(0.0001) - obtained in first place. The fit is robust because the sign of each coefficient is maintained for all the different fits considering all solvents.
-
By performing a coefficient analysis of each independent variable, we saw that some of the solvents could be left out of the analysis. From the plotting of the experimental values versus the calculated values, we also found that there were some solvents that do not follow the regression model. After those solvents were eliminated, the resulting fits were much better. For the new fits, the linear regression model was valid, with a significance superior - F = 47, p(0.0001) - obtained in first place. The fit is robust because the sign of each coefficient is maintained for all the different fits considering all solvents.
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118
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34249059474
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opt are assumed to be the same under both conditions.
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opt are assumed to be the same under both conditions.
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121
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34249058859
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It has to be kept in mind that this equation was derived originally for a model describing a Coulombic interaction between isolated ions that are surrounded by a spherical ion atmosphere. Therefore, it can be only an approximation for more complicated organic molecules, where electron delocalization (resonance effects) may also be present. However, it has already been successfully applied for other covalently linked donor-acceptor molecules; see ref 58
-
It has to be kept in mind that this equation was derived originally for a model describing a Coulombic interaction between isolated ions that are surrounded by a spherical ion atmosphere. Therefore, it can be only an approximation for more complicated organic molecules, where electron delocalization (resonance effects) may also be present. However, it has already been successfully applied for other covalently linked donor-acceptor molecules; see ref 58.
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