Polarizabilities definition

According to the polarizability definition, the difference between the effective charge on the atom A in the complex and that in the free ligand is ... 

This approach to separating the different types of interaetions eontributing to a net solvent effeet has elieited much interest. Tests of the tt, a, and p seales on other solvatochromie or related proeesses have been made, an alternative tt seale based on ehemieally different solvatochromie dyes has been proposed, and the contribution of solvent polarizability to ir has been studied. Opinion is not unanimous, however, that the Kamlet-Taft system eonstitutes the best or ultimate extrathermodynamie approaeh to the study of solvent effeets. There are two objections One of these is to the averaging process by which many model phenomena are eombined to yield a single best-fit value. We eneountered this problem in Section 7.2 when we eonsidered alternative definitions of the Hammett substituent eonstant, and similar eomments apply here Reiehardt has diseussed this in the eontext of the Kamlet-Taft parameters. - The seeond objeetion is to the elaim of generality for the parameters and the eorrelation equation we will return to this eontroversy later. 

It can be seen from Figures 3.7 and 3.8 that the calculations reproduce very well not only the experimental spectra but also the experimentally observed isotopic shifts indicating a high reliability of the computational method. According to this comparison, definite attribution can be made for even the difficult Raman bands that cannot be assigned based solely on the experimental results. It is, however, necessary to mention at this point that the calculated Raman spectrum provided directly by the ab initio computations correspond to the normal Raman spectrum with the band intensity determined by the polarizability of the correlating vibration. Since the intensity pattern exhibited by the experimentally recorded resonance Raman spectrum is due to the resonance enhancement effect of a particular chromophore, with no consideration of this effect, the calculated intensity pattern may, in many... 

Barone, V. Cossi, M. Tomasi, J. A new definition of cavities for the computation of solvation free energies by the polarizable continuum model. J. Chem. Phys. 1997, 107, 3210-3221. 

In order to obtain a definite breakthrough of current across an electrode, a potential in excess of its equilibrium potential must be applied any such excess potential is called an overpotential. If it concerns an ideal polarizable electrode, i.e., an electrode whose surface acts as an ideal catalyst in the electrolytic process, then the overpotential can be considered merely as a diffusion overpotential (nD) and yields (cf., Section 3.1) a real diffusion current. Often, however, the electrode surface is not ideal, which means that the purely chemical reaction concerned has a free enthalpy barrier especially at low current density, where the ion diffusion control of the electrolytic conversion becomes less pronounced, the thermal activation energy (AG°) plays an appreciable role, so that, once the activated complex is reached at the maximum of the enthalpy barrier, only a fraction a (the transfer coefficient) of the electrical energy difference nF(E ml - E ) = nFtjt is used for conversion. 

The fundamental scattering mechanism responsible for ROA was discovered by Atkins and Barron (1969), who showed that interference between the waves scattered via the polarizability and optical activity tensors of the molecule yields a dependence of the scattered intensity on the degree of circular polarization of the incident light and to a circular component in the scattered light. Barron and Buckingham (1971) subsequently developed a more definitive version of the theory and introduced a definition of the dimensionless circular intensity difference (CID),... 

The chemical behavior of ions, ion pairs, and polarizable molecules partakes of the same indistinctness as the definitions of these species. Any attempt to make a complete catalog of the reactions of ions will almost certainly include borderline reactions whose intermediates are in fact ion-pairs or even covalent molecules. For many purposes the identification of a reaction as carbonium ion-like, or what the Germans would call Krypto-ionenreaktion, is as useful as the certain knowledge that the intermediate is actually a carbonium ion. Many of the ionic reaction mechanisms in the literature do not represent actual free ions and were not so intended by their authors. The ionic representation is often merely a convenient simplification if it is an oversimplification it is one that is easily rectified when the pertinent data become available. The value of such approximate mechanisms is that... 

General properties and definitions of polarizabilities can be introduced without invoking the complete DFT formalism by considering first an elementary model the dipole of an isolated, spherical atom induced by a uniform electric field. The variation of the electronic density is represented by a simple scalar the induced atomic dipole moment. This coarse-grained (CG) model of the electronic density permits to derive a useful explicit energy functional where the functional derivatives are formulated in terms of polarizabilities and dipole hardnesses. 

Within the mixed quantum/classical approach, at each time step in a classical molecular dynamics simulation (that is, for each configuration of the bath coordinates), for each chromophore one needs the transition frequency and the transition dipole or polarizability, and if there are multiple chromophores, one needs the coupling frequencies between each pair. For water a number of different possible approaches have been used to obtain these quantities in this section we begin with brief discussions of each approach to determine transition frequencies. For definiteness we consider the case of a single OH stretch chromophore on an HOD molecule in liquid D2O. 

Any molecule has an infinity of excited orbitals in the continuum above the first ionization energy. The electric dipole polarizability is connected partly with a few of these continuum orbitals and partly with the valence orbitals (7). If the simultaneous formation of empty orbitals of X, but with the continuum, it is reasonable to think of M being polarized by X. The population of the continuum orbitals of X is expected to be the more... 

Measurements of dipole moments, Kerr constants, and dielectric absorption have been employed (81RCR336) widely to obtain information on the conformational equilibrium in acyl heterocycles. Details on conformer structures and populations depend on the choice of additive scheme, group moments, or polarizability tensor in the case of Kerr constants. Several early conclusions, especially for furan- and thiophene-2-carboxaldehyde, appeared contradictory, owing to the choice of these quantities. A more precise definition of polarizability tensors for several heterocycles and a choice of group moments and additive schemes tested on a large amount of available experimental results and supported by accurate theoretical calculations have led to more confidence in the use of experimental dipole moments and Kerr constants in conformational analysis. A limitation of the method is that the... 

The second approach to calculating MCD starts from its definition in terms of the real part of first-order correction to the frequency-dependent polarizability in the presence of a magnetic field (Section II.A.6). This definition can be used to consider all types of MCD linear in the magnetic field (9). Our current implementation is restricted to systems with a closed-shell ground state. We shall therefore only consider the calculation of A and terms by this method. 

Erdey-Gruz, 1048, 1306 1474 Erschler, 1133, 1134, 1425 Ethylene oxidation, anodic, 1052 1258 Exchange current density, 1049, 1066 correction of, 1069 definition, 1053 electrocatalysis and, 1278 impedance and, 1136 interfacial reaction, 1047 and partly polarizable interface, 1056 Excited states, lifetime, 1478 Exothermic reaction, 1041 Ex situ techniques, 785, 788, 1146... 

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