Experimental splittings

The fitting of the experimental splitting parameters to a (in the 2 formulation) was fairly successful for LaCl3 and LaA103, but not for La203. 

Referring to Table 6, now, the XH2 systems give very comparable S-T energy splittings for all X (C —> Pb) between the two methods. The most extensively studied system, of course, is CH2 and the experimental splitting there has been measured at... 

TABLE 2. Calculated (UMP2/DZP//TZP) and experimental splitting constants (mT) for some substituted silyl radicals" ... 

The hyperfine splitting constants for all protons of the two benzo[c/ / ]bis-l,3-dioxoles (3) and (4) and benzo[d hydrogen atoms were explained by applying perturbation theory to interaction between the aromatic and heterocyclic ring n MOs <82ZN(A)680>. 

Comparison of Calculated and Experimental Splitting Patterns of Alkali Halide Monomers (in eV)... 

The experimental XANES spectrum has been reported by Li et al. [13] as shown in Fig 7, where the horizontal scale was calibrated by the data obtained by O Brien et al. [28]. As in the case of a-A Oa, the splitting of peak A is attributable to the spin orbit splitting. The calculated splitting of 2p orbital for a free Si atom using the Dirac-Fock-Slater method is 0.66 eV, which agrees well with the experimental splitting (0.6 eV). 

The calculated hyperfine coupling constants (B3LYP/6-31G //MP2/6-31G ) for the type B transition state and the distorted minimum clearly show that this species must be considered a type A structure. The hyperfine coupling pattern of the lowest-energy minimum [ai = —1.43 mT a = 1.98 mT) shows a trend similar to the experimental splittings of the fran.s-l,2-dimethylcyclopropane radical cation a, 2 = —1.19 mT a = 2.18 mT), whereas the pattern calculated for the transition state (fl2,3 = 0.55 mT) is incompatible with that model (Figure 18). The distorted structure type calculated for the methyl-substituted systems seems to prevail also under other conditions (see below). 

The good agreement between the experimental splits and the Koopmans theorem calculated values suggests that the latter method offers a simple, yet approximate, way of calculating Vei for ET and HT processes in a variety of dyads. This proposal has been amply verified [23, 41-46],... 

The upper part of Fig. 8.2 shows the experimental splitting of the 2p i (P) line in silicon at LHeT for increasing stresses along the [100] direction. The... 

The determination of the experimental splitting of the 1 /8 1 round state for the B and Ga acceptors from the attributions of the high-resolution Zeeman spectra gives an ordering, in agreement with those calculated by Broeckx [22], but it shows that the 1/2 sublevels shift linearly with field with a positive gi/2 factor whereas the 3/2 sublevels show nonlinear shifts and splitting,... 

G(d,p) level of theory (including the vibrational spectrum for the ZP correction). The tunneling splittings, accurately computed using a variational method, are shown with the experimental splittings for tropolone in Table 1.2 taken from the article. 

The calculated splitting of the 2H(2)11/2 levels in Er3+ [295] (and Nd3+ [296]) compounds is always smaller than experimental splitting. An empirical correction has been proposed which includes a multiplying factor for the fourth-order diagonal reduced CF matrix element (2H(2) C4 2H(2)). The correction is efficient for 2H(2)n/2 and 2H(2)9/2 and for those levels which are coupled to them by spin-orbit interaction, such as 4I9/2, 4F9/2 and 4Gn/2. With the multiplying factor 1.717, the mean deviation in fitting 58 levels of Cs2NaErCl6 was decreased by 18% [35]. This correction has approximately the same effect as the g40 A operator of the correlation CF. 

Fig. 18 does not lead to a convincing agreement with the observed energy levels. The results of a refined model, taking into account the deviation from Djj symmetry as well as strong through bond interaction with an occupied o MO (e in Djd), are indicated in Fig. 19. The agreement with the experimental splitting pattern is plausible.

The ratios between these parameters, as calculated from the experimental splittings of the doublets of the one-electron spectrum of Ce IV, are... 

Looking at the Grotrian diagrams given in figs. 1.27-1.3 la, one can see that the experimental splittings generally confirm the theory. Two exceptions will be mentioned here. (1) For Ndll 4f ( I)6s, the theory predicts the pairs... 

Then SU(2) is explicitly broken by using different constituent masses for u and d, = 0.300 GeV and = 0.313 GeV, with the results displayed in table 11.1. Also shown are the values obtained with a linear potential model (jS = 1), for which the fit of experimental splittings suggested a much smaller 8/n. 

---