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On the isotropy of induced multipole moments in heavy ion complexes
Author(s) -
Trumm Michael
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25121
Subject(s) - multipole expansion , quadrupole , dipole , isotropy , lanthanide , chemistry , electronic correlation , ab initio , ion , polarization (electrochemistry) , ab initio quantum chemistry methods , atomic physics , tensor (intrinsic definition) , electron , computational chemistry , physics , quantum mechanics , molecule , geometry , mathematics , organic chemistry
Polarization effects have been proven to play an important role in the theoretical description of chemical processes. With this respect, we report ab initio calculations describing multiconfigurational and relativistic effects as well as electron correlation to determine dipole‐ and quadrupole polarizabilities for all trivalent actinide and lanthanide ions. The results are used in an iterative point‐multipole model to compute polarization interaction for different metal compounds. Significant differences between the usage of isotropic polarizabilities for the coordinating ligands compared to the full tensor representation is found. Quadrupole contributions are found to be negligible for symmetric geometries but can contribute up to 30 kJ/mol to the polarization energy in specific cases. The employed method allows a parameter free study of multipole interactions for a wide variety of systems. © 2017 Wiley Periodicals, Inc.