I'm calculating condensed Fukui functions to explain the reactivity of my molecules.

The manual for Multiwfn suggests using atomic dipole moment corrected Hirshfeld charges for it. However I get strange results, on some atoms in which $f^+$ is negative.

I'm using def2-TZVPD basis set, and I'm wondering if diffuse functions can make Hirshfeld charges meaningless as they do for Mulliken charges?

  • $\begingroup$ Some comments were moved to chat (including a link to this related question). Also what @AndrewRosen is talking about is related to this answer by Susi. $\endgroup$ Commented Jun 20, 2021 at 3:42
  • $\begingroup$ Hirshfeld charges are known to be problematic; you should use modern iterative approaches like iterative Stockholder, instead... $\endgroup$ Commented Dec 15, 2021 at 17:31
  • 2
    $\begingroup$ I recommend Minimum Basis iterative Stockholder (MBIS) charges $\endgroup$
    – B. Kelly
    Commented Dec 19, 2021 at 15:31
  • $\begingroup$ Do you have a reference that says that augmenting a basis set causes Mulliken charges to change from meaningful to "meaningless"? $\endgroup$ Commented Feb 7, 2023 at 3:03


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