The Conformational Sensitivity of Iterative Stockholder Partitioning Schemes

T. Verstraelen, P.W. Ayers, V. Van Speybroeck, M. Waroquier
Chemical Physics Letters
545, 138-143


Chemical interpretation and empirical modeling of partial charges requires a robust partitioning scheme to derive these charges from the molecular electronic density. The degree of undesirable conformational sensitivity is assessed for three iterative stockholder partitioning schemes: Hirshfeld-I (HI), Iterative Stockholder Analysis (ISA) and a new Gaussian ISA variant (GISA). GISA has fewer degrees of freedom than ISA and enforces monotonically decaying pro-atoms. These improvements accelerate the converge of GISA as compared to ISA. However, the conformational sensitivity of the charges does not decrease and is still large compared to HI.

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