Subject spectroscopic values

Boron Monoxide and Dioxide. High temperature vapor phases of BO, B2O3, and BO2 have been the subject of a number of spectroscopic and mass spectrometric studies aimed at developiag theories of bonding, electronic stmctures, and thermochemical data (1,34). Values for the principal thermodynamic functions have been calculated and compiled for these gases (35). 

The properties of the hydrogen molecule and molecule-ion which are the most accurately determined and which have also been the subject of theoretical investigation are ionization potentials, heats of dissociation, frequencies of nuclear oscillation, and moments of inertia. The experimental values of all of these quantities are usually obtained from spectroscopic data substantiation is in some cases provided by other experiments, such as thermochemical measurements, specific heats, etc. A review of the experimental values and comparison with some theoretical... 

The measurement of pA bh+ and m values is sometimes complicated by the fact that the spectroscopic methods used (generally H and 13C NMR spectroscopy, and UV-vis) are subject to medium effects. Water and (say) 80 wt% H2SO4 are very different media, and it is not very surprising that spectral peaks for the same species in the two media can occur at different wavelengths or different chemical shifts. Several methods have been devised for handling this problem 24,99,100 the excess acidity method lends itself to dealing with medium effects quite well.101... 

In aqueous solution, thorium exists as Th(IV), and no definitive data have been presented for the presence of lower-valent thorium ions in this medium. The standard potential for the Th(IV)/Th(0) couple has not been determined from experimental electrochemical data. The values presented thus far for the standard reduction potential have been calculated from thermodynamic data or estimated from spectroscopic measurements. The standard potential for the four-electron reduction of Th(IV) ions has been estimated as —1.9 V in two separate references 12. The reduction of Th(OH)4 to Th metal was estimated at —2.48 V in the same two publications. Nugent et al. calculated the standard potential for the oxidation ofTh(III) to Th(IV) as +3.7 V versus SHE, while Miles provides a value of +2.4 V [13]. The standard potential measurements from studies in molten-salt media have been the subject of some controversy. The interested reader is encouraged to look at the summary from Martinot [10] and the original references for additional information [14]. 

If a free-atom state (Section 6.3.3) is subject to a magnetic field the (2J + l)-fold degeneracy is lifted so that, as shown in Figure 27, each level specified by the quantum number My is separated from its neighbour by the amount gjpH, where gj is the spectroscopic splitting factor. The value of g can be calculated from a knowledge of the term from which the state arose. 

However, spectroscopic studies of activated BLM indicate that it is not an Fev=0 species. It exhibits an S - 1/2 EPR spectrum with g values at 2.26, 2.17, and 1.94 [15], which is typical of a low-spin Fe111 center. This low-spin Fem designation is corroborated by Mossbauer and x-ray absorption spectroscopy [16,19], Furthermore, EXAFS studies on activated BLM show no evidence for a short Fe—0 distance, which would be expected for an iron-oxo moiety [19], These spectroscopic results suggest that activated BLM is a low-spin iron(III) peroxide complex, so the two oxidizing equivalents needed for the oxidation chemistry would be localized on the dioxygen moiety, instead of on the metal center. This Fe(III)BLM—OOH formulation has been recently confirmed by electrospray ionization mass spectrometry [20] and is supported by the characterization of related synthetic low-spin iron(III) peroxide species, e.g., [Fe(pma)02]+ [21] and [Fe(N4py)OOH]2+ [22], The question then arises whether the peroxide intermediate is itself the oxidant in these reactions or the precursor to a short-lived iron-oxo species that effects the cytochrome P-450-like transformations. This remains an open question and the subject of continuing interest. 

For HCN the situation is somewhat better, because the data on DCN are much more effectively independent of the HCN data. This molecule has also been the subject of much high-resolution spectroscopic study, so that the vibration-rotation energy levels are particularly well known and its vibrational spectrum is free of accidental resonances. Table 8 compares the results of three quite different calculations. The calculation by Strey and Mills is the most recent, and was based on the latest spectroscopic data the refinement was made to a and x values rather than to the vibrational levels and rotational constants as used by both the earlier workers. Strey and Mills also constrained 3 of the quartic interaction constants to zero, and refined to cubic and quartic force constants in a separate calculation to the quadratic refinement. The level of agreement between the calculations leads to conclusions rather similar to those made above for C02 in particular, standard errors should be multiplied by at... 

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