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ealanis

Member

Registered: 2026-03-25

Posts: 3

Discrepancy in Hirshfeld charges between ORCA 6.1 output and Multiwfn

Hello everyone,

I am encountering a discrepancy between the Hirshfeld charges reported directly by ORCA and those computed by Multiwfn when reading the wavefunction from the same ORCA calculation.

For example for the Tb atom Multiwfn output: The Hirshfeld charge for Tb is 1.054099, while the Hirshfeld charge reported by orca is  0.683571.

Im using ORCA 6.1 and multiwfn Version 3.8.

find attached a dropbox link for the molden.input file and both orca and Multiwfn outputs: https://www.dropbox.com/scl/fi/30c0ij4f … vkygj&dl=0

I want to ensure that the charges I use for further analysis are consistent and accurate, e.g. I computed CM5 charges but noticed the discrepancy in the Hirshfeld analysis. Any insights would be greatly appreciated.

Thank you in advance for your help!

sobereva

Tian Lu (Multiwfn developer)

From: Athens, Greece

Registered: 2017-09-11

Posts: 2,217

Website

Re: Discrepancy in Hirshfeld charges between ORCA 6.1 output and Multiwfn

Calculation of Hirshfeld charges needs electron density of atoms in their isolated states. However, there is no unique way of generating them. I am not sure how ORCA developers generated them and cannot comment on it, what I can say is that the Hirshfeld charge in Multiwfn was implemented in a very rigorous way, and the quality of built-in atomic densities in isolated states has a very high quality (see Section 6.3 of Multiwfn manual for details). So, as long as the wavefunction and structure you provided to Multiwfn are correct, and the commands you inputted in Multiwfn are correct, the Hirshfeld charges computed by Multiwfn must be correct.

BTW: It is suggested to first check if Mulliken charges calculated by Multiwfn and ORCA are the same; if they are the same, that means the wavefunction has been correctly passed to Multiwfn.

ealanis

Member

Registered: 2026-03-25

Posts: 3

Re: Discrepancy in Hirshfeld charges between ORCA 6.1 output and Multiwfn

Calculation of Hirshfeld charges needs electron density of atoms in their isolated states. However, there is no unique way of generating them. I am not sure how ORCA developers generated them and cannot comment on it, what I can say is that the Hirshfeld charge in Multiwfn was implemented in a very rigorous way, and the quality of built-in atomic densities in isolated states has a very high quality (see Section 6.3 of Multiwfn manual for details). So, as long as the wavefunction and structure you provided to Multiwfn are correct, and the commands you inputted in Multiwfn are correct, the Hirshfeld charges computed by Multiwfn must be correct.

BTW: It is suggested to first check if Mulliken charges calculated by Multiwfn and ORCA are the same; if they are the same, that means the wavefunction has been correctly passed to Multiwfn.

Thank you for your quick response, I see the problem now. Orca uses a different approach to compute the reference densities. Now, it seems to me that I should stick to Multiwfn values. Nevertheless, the CM5 charges have a rather odd discontinuity with the Tb complex (I have 15 Ln-MDH complexes with Ln = La-Lu). Reading the Section 6.3 I see that it is possible to replace built-in atomic density of Tb for example. I have computed it at wb97m-d4rev/x2c-TZVPPall level of theory and have sucesfuly generated the sphavgval.txt file. Now, I dont find the location of atmraddens.f90 in order to copy the information of the new density generatted in sphavgval.txt file.

Where is this file located?

sobereva

Tian Lu (Multiwfn developer)

From: Athens, Greece

Registered: 2017-09-11

Posts: 2,217

Website

Re: Discrepancy in Hirshfeld charges between ORCA 6.1 output and Multiwfn

atmraddens.f90 file can be found in the source code package of Multiwfn, in this file you can find "subroutine genatmradpos", which defines radial density for all elements. After replacing the existing data of Tb by the data in sphavgval.txt, you need to recompile Multiwfn to make the modification take effect.

ealanis

Member

Registered: 2026-03-25

Posts: 3

Re: Discrepancy in Hirshfeld charges between ORCA 6.1 output and Multiwfn

atmraddens.f90 file can be found in the source code package of Multiwfn, in this file you can find "subroutine genatmradpos", which defines radial density for all elements. After replacing the existing data of Tb by the data in sphavgval.txt, you need to recompile Multiwfn to make the modification take effect.

Thank you, I really appreciate the guidance. The Ln complexes are trivalent though. Do I need to generate the reference densities in this Oxidation state, i.e. as Ln(III)? Or in the neutral ground state configuration.

sobereva

Tian Lu (Multiwfn developer)

From: Athens, Greece

Registered: 2017-09-11

Posts: 2,217

Website

Re: Discrepancy in Hirshfeld charges between ORCA 6.1 output and Multiwfn

atmraddens.f90 file can be found in the source code package of Multiwfn, in this file you can find "subroutine genatmradpos", which defines radial density for all elements. After replacing the existing data of Tb by the data in sphavgval.txt, you need to recompile Multiwfn to make the modification take effect.

Thank you, I really appreciate the guidance. The Ln complexes are trivalent though. Do I need to generate the reference densities in this Oxidation state, i.e. as Ln(III)? Or in the neutral ground state configuration.

must in the neutral ground state configuration, according to the definition of Hirshfeld method