Multipole moments effective

Many authors [8-10] have demonstrated that the CP method undercorrects the BSSE. Moreover, Karlstrom and Sadlej [11] pointed out that addition of the partner orbitals to the basis set of a molecule not only lowers its energy, in accordance with the variation principle, but also affects the monomer properties (multipole moments and polarizabilities). Latajka and Scheiner [12] found that in a model ion-neutral system such as Li" -OH2, this secondary BSSE can be comparable in magnitude to the primary effect at both SCF and MP2 levels. The same authors also underlined the strong anisotropy of secondary error [13]. 

Representation of the density n(r) [or, effectively, the electrostatic potential — 0(r)] near any one of the sinks as an expansion in the monopole and dipole contribution only [as in eqn. (230c)] is generally, unsatisfactory. This is precisely the region where the higher multipole moments make their greatest contribution. However, the situation can be improved considerably. Felderhof and Deutch [25] suggested that the physical size of the sinks and dipoles be reduced from R to effectively zero, but that the magnitude of all the monopoles and dipoles, p/, are maintained, by the definition... 

A = J —J f. Here the Dyakonov tensor <1>q characterizes the polarization of the registered light. In deriving Eq. (2.24) the properties of the 17-functions were used, as previously in the case of Eq. (2.21) and according to (A.13) and (B.4). It may thus be seen from (2.24) that only the multipole moments bpQ of rank K < 2 have any direct effect on the intensity and polarization of molecular fluorescence. This latter assertion also holds in the case where multipole moments of rank higher than K = 2 are created in the excited state (6) in the case of absorption of sufficiently intensive light. 

If we assume the lower level Lande factor as known, then the fit of non-linear Hanle signals permits us to determine the relaxation constants 7K = 7, as well as the effective cross-sections light field, which mixes the multipole moments aPq with different k, does not permit us to determine the values for definite k separately. Nevertheless (Section 3.3), the discrepancies between the 7K values are negligible in many cases, and the information obtained is sufficiently reliable. 

Solvent continuum models are now routinely used in quantum mechanical (QM) studies to calculate solvation effects on molecular properties and reactivity. In these models, the solvent is represented by a dielectric continuum that in the presence of electronic and nuclear charges of the solute polarizes, creating an electrostatic potential, the so-called reaction field . The concept goes back to classical electrostatic schemes by Martin [1], Bell [2] and Onsager [3] who made fundamental contributions to the theory of solutions. Scholte [4] and Kirkwood [5] introduced the use of multipole moment distributions. The first implementation in QM calculations was reported in a pioneer work by Rivail and Rinaldi [6,7], Other fundamental investigations were carried out by Tapia and Goscinski [8], Hilton-McCreery et al. [9] and Miertus et al. [10], Many improvements have been made since then (for a review,... 

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