Effects analysis model, explanation

The analysis of variance (ANOVA) gives information on the significant effects. Data were analyzed using the general linear model (GLM) procedure from the Statistical Analysis System (SAS Institute, Cary, NC). A discussion and explanation of the statistics involved are given by Davies [19]. 

Since the Marcus model was initially a classical or later a semi-classical theory, the introduction of quantum effects was considered to account for these observations. In particular, tunnelling pathways of e.t. would increase the rates of some reactions. A closer analysis has, however, led to the conclusion that this could not be a general explanation [80]. 

Whereas the proton transfer does not effect the stochiometry of the final PI when water is eliminated in the imidization reaction (fig. 3F), addition of an excess ODA molecule to polyamic acid could lead to the imine type crosslink formation schematically shown in figure 3G. This would lead to a deficiency of carbonyl oxygen atoms for vapor deposited polyimide and is consistent with our analysis. Mack et al. [16] proposed imine crosslink formation from their Raman spectroscopic studies for vapor deposited polyimides with excess ODA. In accordance with this model we attribute the low binding energy shoulder in the polyimide Nls line (figure 4c) to double bonded nitrogen species. However, the model gives no explanation for the carbonyl deficiency found in spin deposited polyamic acid and polyimide. In this case no excess of ODA is observed and only a very weak shoulder has been reported for the Nls line [4,11]. 

The concept of steric effects, an extremely important component of the modem theory of organic chemistry, is based upon an oversimplified assumption which considers organic molecules in terms of ball-and-stick models. The latter seem to be absolutely inadequate or even basically incorrect from the point of view of quantum chemistry. Nevertheless, the imaginative and insightful application of this approach enabled organic chemists to start to develop conformational analysis as one of the most fruitful theories of modern organic chemistry, capable not only of explanation but also of prediction of chemical phenomena. 

The ECL mechanism for both Ru(bpy)3" and Ru(dph) + complexes seems to be parallel, with one important difference. In the case of Ru(bpy)3 , the efficiency increases as temperature decreases. The opposite trend is observed for Ru(dph) " . The effects are rather small, but certainly greater than the experimental errors. The trivial explanation that the observed difference is caused by medium effects can be simply excluded. Our unpublished results indicate that the ECL behavior of Ru(bpy)3+ in both solvents (ACN and BN) is nearly the same. The observed difference can be understood by kinetic analysis in terms of the electron transfer model for ECL processes. According to this model, the yield of the emissive excited state is given by the ratio of the rate constants for the electron transfer processes producing the excited-state and the ground-state products, respectively. Unfortunately, the values of the appropriate parameters, which are necessary for the calculation of these rates, are not available. However, some qualitative conclusions are possible they are summarized below. 

Calculations at the B3LYP/6-31G level were used to show how hydrogen bond formation influences the chemical reactivity of ketones.70 The effect of the chloroform on the activation energies was modelled by means of discrete-continuum models. Explicit hydrogen bond formation to chloroform lowers the gas-phase activation barrier. A DFT analysis of the global electrophilicity of the reagents provided a sound explanation of the catalytic effects of chloroform (see Table 6 and Chart 3). The electrophilicity of acetone... 

---