Chemical shift polarizabilities

In this respect, the solvatochromic approach developed by Kamlet, Taft and coworkers38 which defines four parameters n. a, ji and <5 (with the addition of others when the need arose), to evaluate the different solvent effects, was highly successful in describing the solvent effects on the rates of reactions, as well as in NMR chemical shifts, IR, UV and fluorescence spectra, sol vent-water partition coefficients etc.38. In addition to the polarity/polarizability of the solvent, measured by the solvatochromic parameter ir, the aptitude to donate a hydrogen atom to form a hydrogen bond, measured by a, or its tendency to provide a pair of electrons to such a bond, /, and the cavity effect (or Hildebrand solubility parameter), S, are integrated in a multi-parametric equation to rationalize the solvent effects. 

This approach has also been applied to saturated C(i) atoms. Due to the much lower polarizabilities of C-H and C-C single bonds, however, the effects are clearly smaller (82), though still detectable. Thus, some effects of substituents X on S-positioned carbon atoms in cyclohexanes and cholestanes were attributed to LEF effects of the C-X dipoles by Schneider and colleagues (76,77,85). The finding that only minor effects are to be expected in saturated molecules was confirmed by INDO-SCF calculations of electric-field effects on l3C chemical shifts of some model compounds performed by Seidman and Maciel (86). These authors conclude, further, that conformational studies on such systems are not promising (86). 

Abstract Although the electronic structure and the electrical properties of molecules in first approximation are independent of isotope substitution, small differences do exist. These are usually due to the isotopic differences which occur on vibrational averaging. Vibrational amplitude effects are important when considering isotope effects on dipole moments, polarizability, NMR chemical shifts, molar volumes, and fine structure in electron spin resonance, all properties which must be averaged over vibrational motion. 

From the fit one obtains values of and a. Note how the electronic polarizability of the adsorbed molecules gives the absorptance a nonlinear coverage dependence. However, there exist several systems that do not follow Eqs. (2) and (3). This can be caused either by a coverage dependent change in the electronic structure, that is an additional chemical shift, or because the system exhibits clustering or the molecules occupy more the one adsorption site, since the theory assumes a random filling of the adsorbate lattice. 

The observed regioselectivity of the addition of asymmetrically substituted olefins RCH=CH2 (R = Me, OH, CO2H, CN, Cl, etc.) was rationalized in terms of the magnitude of the electronic effect, calculated by using the "C NMR chemical shifts for monosubstituted benzene and polarizability."... 

The above data have been analyzed theoretically within the same model as described for the chemical shift tensor (5iso In order to understand the chemical shift observed within the KDP family, we concentrate here on the polarizability modified double-well potential of the protons, which has been modelled by two back-to-back Morse potentials (see Chap. 1 in this volume). The separation between the protons and the centre of the left (/) or right (r) PO4 shell... 

Atomic xenon, with its large polarizability, has chemical shifts extremely sensitive to its physical surroundings. Using isotope Xenon-129 as a probe, Ito and Fraissard proposed [4] that the °Xe chemical shifts of xenon adsorbed on a zeolite can be written as... 

The dynamics of the molecules adsorbed in confined geometry is one of the most common and important research subject which has received much attention in the past few decades. Owing to the large polarizability and the chemical inert nature of the monoatomic xenon, the l29Xe NMR chemical shift is very sensitive to its environment and thus provides an ideal probe for the investigation of the structure of porous materials [1]. There have been numerous publications in this area since the pioneering works by Ito and Fraissard [2] and by Ripmeester [3], and several reviews have been attributed to related subjects [4-7]. Recent developments of the mesoporous MCM-41 materials [8] have also drawn intense attention due... 

A linear correlation between 13C chemical shifts and local n electron densities has been reported for monocyclic (4n + 2) n electron systems such as benzene and nonbenzenoid aromatic ions [76] (Section 3.1.3, Fig. 3.2). In contrast to theoretical predictions (86.7 ppm per n electron [75]), the experimental slope is 160 ppm per it electron (Fig. 3.2), so that additional parameters such as o electron density and bond order have to be taken into account [381]. Another semiempirical approach based on perturbational MO theory predicts alkyl-induced 13C chemical shifts in aromatic hydrocarbons by means of a two-parameter equation parameters are the atom-atom polarizability nijt obtained from HMO calculations, and an empirically determined substituent constant [382]. 

Several approaches have been made to calculate 13C chemical shifts of coumarins by MO methods. Good correlations were found between the 13C chemical shift values of coumarin (also protonated) and the n charge densities calculated by the CNDO/2 method [962], and of coumarins with it charge densities calculated by the Hiickel MO method (which, however, fails for methoxylated coumarins) [965]. Chemical shifts of mono- and dimethoxycoumarins have been correlated with parameters determined by refined INDO MO calculations, in which n bond orders, atom-atom polarizabilities, excitation energies and electron-nucleus distances were taken into consideration [966], In 3-substituted 4-hydroxy and 4-hydroxy-7-methoxycoumarins chemical shifts were found to be related to Swain and Lupton s parameters iF and M [388], according to equation 5.4 (SE = Substitution Effect) ... 

With the advent of reliable, readily available, molecular modeling packages there has been an increase in the number of reports that compare and contrast theoretical geometries and conformations, orbital charge, polarizabilities, and NMR chemical shifts with experimental values. A selection of theoretical methods and the type of information thus obtained on six-membered sulfur heterocycles is presented in Table 1. 

Since the suggestion of the sequential QM/MM hybrid method, Canuto, Coutinho and co-authors have applied this method with success in the study of several systems and properties shift of the electronic absorption spectrum of benzene [42], pyrimidine [51] and (3-carotene [47] in several solvents shift of the ortho-betaine in water [52] shift of the electronic absorption and emission spectrum of formaldehyde in water [53] and acetone in water [54] hydrogen interaction energy of pyridine [46] and guanine-cytosine in water [55] differential solvation of phenol and phenoxy radical in different solvents [56,57] hydrated electron [58] dipole polarizability of F in water [59] tautomeric equilibrium of 2-mercaptopyridine in water [60] NMR chemical shifts in liquid water [61] electron affinity and ionization potential of liquid water [62] and liquid ammonia [35] dipole polarizability of atomic liquids [63] etc. 

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