Anisotropic value

Tile ESR spectra of the radical anions, generated by one-electron reduction of the a-oxothioketone 173 and the dithiete 172, were determined, and spin densities were calculated from the coupling constants and, especially, from the anisotropic values (87CB575). 

The dipole and quadrupole polarizability tensor components of LiH were calculated by MCSCF linear response theory with the basis set of Roos and Sadlej [57] which consists of 13s-, 8p-, 6d-, and 2f-type sets of uncontracted Gaussian functions on Li and 12s-, 8p-, and 5d-type sets of uncontracted Gaussians on H. Due to the small size of the molecule we could perform MCSCF calculations over the whole range of internuclear distances with a very large CAS 0000 520,10,10,4 p g present the tensor components, isotropic, and anisotropic values of the dipole polarizability tensor a as function... 

For the above case this results in the corresponding highly anisotropic values Ka — 675, Kb = 234, and Kc — 15 reflecting the very short mean free paths in the b and c directions. According to the weak couphng or short coherence length in the c direction the critical current, jc = 0.1 A/cm, is approximately one order of magnitude smaller than in the a direction [112]. 

Chemical shift anisotropy (CSA) linear with Ho ("Chemical diagnostic") isotropic values anisotropic values up to 10 kHz... 

AJ — Jz z l/ ( fx A/ "b yy and Jx x " yy were compared with the experimentally determined values. Here, the z axis is parallel with the molecular symmetry axis. A very good agreement was obtained between the calculated and experimental isotropic couplings, and a reasonable agreement was found for the anisotropic values. For example, in the case of CHF3, the calculated and experimental values for A /(F, F) are —232 Hz and —200 Hz, respectively. 

Mn(H20)6] , but we omitted anisotropic values because the anisotropic values are not observed with the EPR experiment for solutions [53]. For these complexes, the dependence of all H °values on XC functionals is similar all DFT and hybrid DFT underestimate values, while HF overestimates the 1 ° value. As for global hybrid DFT such as B3LYP and TPSSh, the results we obtained are similar to those showed in previous studies [21, 22], Even if we employed any range-separated... 

The and the Na hyperfine interactions were finally employed to obtain the spin densities in the molecular orbitals of the NO-Na" complex to give insight into the electronic structure of the adsorption complex. An isotropic /r/coupling of Aiso( Na) = 7.8 MHz was evaluated from the above principal values of the A( Na) tensor. From the Aiso( Na) value an unpaired electron spin density in the Na 3s orbital is evaluated to be /03s(Na) = 0.9% [34]. In addition, judging from the small anisotropic values of the A( Na) tensor, Bzz( Na) = A - Aiso = 3.1 0.2 MHz, the spin density in Na 3p orbitals is negligible. Thus, the unpaired electron in the Na" -NO complex is concluded to be mainly localized at the NO molecule. 

Note Where the fitxes are anisotropic, values given refer to the fitjre axis direction, except values In parenthesis which refer to the radial direction. The data all refer to 20°C, and . 

Since it is known that the isotropic splitting for a Hartree 2s atomic orbital on carbon is about 3110 MHz (Morton, 1964), we have p2s = 7.4/3110 = 2 X 10 . (Spin densities in triplet states are typically normalized to unity.) The anisotropic part is nearly cylindrical about the x" axis, and clearly derives mainly from the carbon 2pn electron. If we compare the value 37.3 MHz with the anisotropic value for a 2p atomic orbital on carbon ( 182 MHz), we have p2 = 0.20. The residual anisotropy in Eq. (42) is small. 

The non-hydrogen atoms were refined with anisotropic thermal parameters.32 Hydrogen atom positions were calculated with the use of a C-H distance of 0.96 A and an isotropic thermal parameter calculated from the anisotropic values for the atoms to which they were connected. Final least squares refinement resulted in residuals of R = 5.9% and R =... 

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