Considerations for Lanthanides

It turned out that for the CD bases, errors in bond energies are in the same range as those obtained with def2-TZVP bases (MP2 def2-TZVPP) for the rest of the periodic table. Further it became evident that the comparably large g set of the CD bases be reduced for most cases, as shown below. For dipole moments in contrast, errors of CD bases were very large, e.g., for HF 0.561 0.533, which is below double zeta quality. The reason for this turned out to be a missing diffuse p function. 

QZVP/PP (16s18p11 d100/[11 s8p6d5f] (3g)/[2gl (6g1h)/[3g1h] 118/151 138/187 

and QZVPP basis sets (from left to right, characterized by their numb j of spherical harmonic basis functions) for the molecules of the test set at levels DFT(BP86), upper part and MP2, lower part 

For more detailed statistics and data for single compounds we refer to the publications about the def2-bases for the lanthanides, [25] and for the other elements, [10] as well as to that about the dhf-bases. [21] All def2-bases are available from the internet at http //www.cosmologic.de/basis-sets/basissets.php. 

Ahlrichs R, Scharf P, and Jankowski K. 1985. The impact of higher polarization basis functions on molecular ah-initio results. 2. The ground states of CO, N2, NO, 02 and F2. Chem. Phys. 98, 381-386. 

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Spectrophotometric experiments, however, do not provide straightforward evidence for the existence of small amounts of americium hydroxypolymers. In order to compare the literature data with one another and with our data, they are transformed to thermodynamic data at I = 0 according to Baes and Mesmer (1), using the salt effect constants assessed by them. These data are given in parentheses in Table I. The first hydrolysis constants given in the literature differ from one another considerably. For lanthanide ions, log Bi values are reported from 3.7 to 6.3 (1), which are distinctly lower than that of americium shown in Table I. 

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