Libraries of Extremely Localized Molecular Orbitals. 2. Comparison with the Pseudoatoms Transferability

Abstract : Due to both technical and methodological difficulties, determining and analyzing charge densities of very large molecular systems represents a serious challenge that, in the crystallographers community, has been mainly tackled by observing that the so-called pseudoatoms of the electron density multipole expansions are reliably transferable from molecule to molecule. This has led to the construction of pseudoatoms databanks that have allowed successful refinements of crystallographic structures of macromolecules, while taking into account their corresponding reconstructed electron distributions. A recent alternative/complement to the previous approach is represented by techniques based on extremely localized molecular orbitals (ELMOs) that, due to their strict localization on small molecular fragments (e.g., atoms, bonds, and functional groups), are also in principle exportable from system to system. The ELMOs transferability has been already tested in detail, and, in this work, it has been compared to the one of the pseudoatoms. To accomplish this task, electron distributions obtained both through the transfer of pseudoatoms and through the transfer of extremely localized molecular orbitals have been analyzed, especially taking into account topological properties and similarity indexes. The obtained results indicate that all the considered reconstruction methods give completely reasonable and similar charge densities, and, consequently, the new ELMOs libraries will probably represent new useful tools not only for refining crystal structures but also for computing approximate electronic properties of very large molecules.
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Benjamin Meyer, Benoît Guillot, Manuel F. Ruiz-Lopez, Christian Jelsch, Alessandro Genoni. Libraries of Extremely Localized Molecular Orbitals. 2. Comparison with the Pseudoatoms Transferability. Journal of Chemical Theory and Computation, American Chemical Society, 2016, 12 (3), pp.1068-1081. ⟨10.1021/acs.jctc.5b01008⟩. ⟨hal-01532025⟩



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