I was about to post wfn_results.xlsx this spreadsheet file with the results of the calculations I've done overnight. Column A is the compound name (all are dianions), columns B to M are number of electrons expected to be found. Columns O to U are what 17 1 9 4 12 finds (blue colored refers to water solvent systems). It seems that the error is always in one basin (core or valence). I will now download the latest version and re run the calculations.

May I ask though, how are core electrons treated when ECP is present? The program detects "Total/Alpha/Beta electrons correctly, but in the 17 19 4 12 integration it seems to find roughly total core populatons without ECP - ~ 5 electrons.

Be2F6_dianion_water.wfn

Some testing though seems that Be2Cl6 and Be2Br6 in water are just fine. And is some issue with this particular wnf file perhaps.

An update: The error seems to be only with the Be2F6 in water and only with the option "Assign ELF basin labels" (input sequence 17 1 9 (1-4) 12). Using a sequence "2 Integrate real space functions in the basins 9 ELF" during the same job yields valid results. Somehow, option 12 adds ~17 electrons to one of the basins.

Here is copy of the terminal output ([Be2F6]2- (64 e), in water) from a low quality grid just for showing quickly the results, basin 21 is the problematic one: (first tests show the problematic basin changes each run)

12
Assigning labels for core basins...
Assigning labels for valence basins...
Progress: [##################################################]   100.0 %     /
Evaluating basin populations and volumes, please wait...
Progress: [##################################################]   100.0 %     |

The following information is printed according to basin indices
Basin indices, populations (e), volumes (Angstrom^3) and assigned labels:
Basin    1  Pop.:  6.2712  Vol.:  198.400  Label: V(F8)
Basin    2  Pop.:  4.9320  Vol.:   80.681  Label: V(F2)
Basin    3  Pop.:  4.9320  Vol.:   76.561  Label: V(F6)
Basin    4  Pop.:  6.2712  Vol.:  202.918  Label: V(F4)
Basin    5  Pop.:  2.2368  Vol.:    0.040  Label: C(F8)
Basin    6  Pop.:  2.2368  Vol.:    0.040  Label: C(F4)
Basin    7  Pop.:  1.3316  Vol.:    1.693  Label: V(Be5,F8)
Basin    8  Pop.:  1.3445  Vol.:    1.923  Label: V(F2,Be5)
Basin    9  Pop.:  1.3316  Vol.:    1.693  Label: V(Be1,F4)
Basin   10  Pop.:  1.3445  Vol.:    1.920  Label: V(Be5,F6)
Basin   11  Pop.:  1.3445  Vol.:    1.924  Label: V(Be1,F2)
Basin   12  Pop.:  1.3445  Vol.:    1.920  Label: V(Be1,F6)
Basin   13  Pop.:  6.3454  Vol.:  202.133  Label: V(F7)
Basin   14  Pop.:  2.0434  Vol.:    0.650  Label: C(Be5)
Basin   15  Pop.:  1.9907  Vol.:    0.040  Label: C(F2)
Basin   16  Pop.:  1.9907  Vol.:    0.040  Label: C(F6)
Basin   17  Pop.:  2.0434  Vol.:    0.650  Label: C(Be1)
Basin   18  Pop.:  6.3454  Vol.:  206.630  Label: V(F3)
Basin   19  Pop.:  1.2627  Vol.:    1.581  Label: V(Be5,F7)
Basin   20  Pop.:  1.2627  Vol.:    1.581  Label: V(Be1,F3)
Basin   21  Pop.: 17.9989  Vol.:    0.040  Label: C(F7)
Basin   22  Pop.:  2.0149  Vol.:    0.040  Label: C(F3)

Sum of core basin populations:        32.5556
Sum of valence basin populations:     45.6637
Sum of all basin populations:         78.2193

Sorting basins according to labels...
The following information is printed according to order of basin labels
Basin indices, populations (e), volumes (Angstrom^3) and assigned labels
#    1  Basin   22  Pop.:  2.0149  Vol.:    0.040  Label: C(F3)
#    2  Basin   21  Pop.: 17.9989  Vol.:    0.040  Label: C(F7)
#    3  Basin   17  Pop.:  2.0434  Vol.:    0.650  Label: C(Be1)
#    4  Basin   16  Pop.:  1.9907  Vol.:    0.040  Label: C(F6)
#    5  Basin   15  Pop.:  1.9907  Vol.:    0.040  Label: C(F2)
#    6  Basin   14  Pop.:  2.0434  Vol.:    0.650  Label: C(Be5)
#    7  Basin    6  Pop.:  2.2368  Vol.:    0.040  Label: C(F4)
#    8  Basin    5  Pop.:  2.2368  Vol.:    0.040  Label: C(F8)
#    9  Basin   18  Pop.:  6.3454  Vol.:  206.630  Label: V(F3)
#   10  Basin    3  Pop.:  4.9320  Vol.:   76.561  Label: V(F6)
#   11  Basin   13  Pop.:  6.3454  Vol.:  202.133  Label: V(F7)
#   12  Basin    2  Pop.:  4.9320  Vol.:   80.681  Label: V(F2)
#   13  Basin    4  Pop.:  6.2712  Vol.:  202.918  Label: V(F4)
#   14  Basin    1  Pop.:  6.2712  Vol.:  198.400  Label: V(F8)
#   15  Basin   11  Pop.:  1.3445  Vol.:    1.924  Label: V(Be1,F2)
#   16  Basin   20  Pop.:  1.2627  Vol.:    1.581  Label: V(Be1,F3)
#   17  Basin    9  Pop.:  1.3316  Vol.:    1.693  Label: V(Be1,F4)
#   18  Basin   12  Pop.:  1.3445  Vol.:    1.920  Label: V(Be1,F6)
#   19  Basin    8  Pop.:  1.3445  Vol.:    1.923  Label: V(F2,Be5)
#   20  Basin   10  Pop.:  1.3445  Vol.:    1.920  Label: V(Be5,F6)
#   21  Basin   19  Pop.:  1.2627  Vol.:    1.581  Label: V(Be5,F7)
#   22  Basin    7  Pop.:  1.3316  Vol.:    1.693  Label: V(Be5,F8)

Number of core basins is     8, their indices:
5,6,14-17,21,22
Number of  1-synaptic basins is     6, their indices:
1-4,13,18
Number of  2-synaptic basins is     8, their indices:
7-12,19,20

                  ============= Basin analysis =============
-10 Return to main menu
-6 Set parameter for attractor clustering or manually perform clustering
-45 Export attractor information and cube file of present grid data
-5 Export basins as cube file
-4 Export attractors as pdb/pqr/txt/gjf file
-3 Show information of attractors
-2 Measure distances, angles and dihedral angles between attractors or atoms
-1 Select the method for generating basins
  0 Visualize attractors and basins
  1 Regenerate basins and relocate attractors
  2 Integrate real space functions in the basins
  3 Calculate electric multipole moments and <r^2> for basins
  4 Calculate localization index (LI) and delocalization index (DI) for basins
  5 Output orbital overlap matrix in basins to BOM.txt in current folder
10 Calculate high ELF localization domain population and volume (HELP, HELV)
11 Calculate orbital compositions contributed by various basins
12 Assign ELF basin labels
2

Please select the integrand:
-2 Return
-1 The values of the grid data stored in an external file (.cub/.grd)
0 The values of the grid data stored in memory
             ----------- Available real space functions -----------
1 Electron density (rho)     2 Gradient norm of rho     3 Laplacian of rho
4 Value of orbital wavefunction         44 Orbital probability density
5 Electron spin density
6 Hamiltonian kinetic energy density K(r)
7 Lagrangian kinetic energy density G(r)
8 Electrostatic potential from nuclear charges
9 Electron localization function (ELF)
10 Localized orbital locator (LOL)
11 Local information entropy
12 Total electrostatic potential (ESP)
13 Reduced density gradient (RDG)       14 RDG with promolecular approximation
15 Sign(lambda2)*rho      16 Sign(lambda2)*rho with promolecular approximation
17 Correlation hole for alpha, ref. point:   0.00000   0.00000   0.00000
18 Average local ionization energy (ALIE)
19 Source function, mode: 1, ref. point:   0.00000   0.00000   0.00000
20 Electron delocal. range func. EDR(r;d)  21 Orbital overlap dist. func. D(r)
22 Delta-g (promolecular approximation)    23 Delta-g (Hirshfeld partition)
24 Interaction region indicator (IRI)    25 van der Waals potential (probe=C )
100 User-defined function (iuserfunc=    0), see Section 2.7 of manual
1
Integrating, please wait...
Progress: [##################################################]   100.0 %     \
   #Basin        Integral(a.u.)      Volume(a.u.^3)
       1          6.2711728011       1338.87200000
       2          4.9320407832        544.46400000
       3          4.9320349937        516.65600000
       4          6.2711766577       1369.36000000
       5          2.2368212255          0.27200000
       6          2.2368212255          0.27200000
       7          1.3316213589         11.42400000
       8          1.3444968056         12.97600000
       9          1.3316213589         11.42400000
      10          1.3444968055         12.96000000
      11          1.3444968057         12.98400000
      12          1.3444968055         12.96000000
      13          6.3453661586       1364.06400000
      14          2.0433783222          4.38400000
      15          1.9906591894          0.27200000
      16          1.9906591894          0.27200000
      17          2.0433783222          4.38400000
      18          6.3453687602       1394.40800000
      19          1.2626604030         10.67200000
      20          1.2626604030         10.67200000
      21          2.0149239202          0.27200000
      22          2.0149239202          0.27200000
Sum of above values:         62.23527622
Integral of the grids travelled to box boundary:          0.00000009
Integrating basins took up wall clock time         1 s

.wfn file produced under implicit solvation model can be normally analyzed by Multiwfn.

ELF gradient is calculated analytically in Multiwfn.

Running 17 1 9 4 12 on a [Be2F6]2- wfn file obtained with SCRF(SMD, solvent=water) in Gaussian16, results in a population of ~81 electrons. Be2F6 in vacuum results in 64.0 electrons as it should.

Here is part of the output:

The following information is printed according to basin indices
Basin indices, populations (e), volumes (Angstrom^3) and assigned labels:
Basin    1  Pop.:  3.5680  Vol.:  139.506  Label: V(F7)
Basin    2  Pop.:  3.6193  Vol.:  133.044  Label: V(F8)
Basin    3  Pop.:  2.7588  Vol.:   42.311  Label: V(F2)
Basin    4  Pop.:  2.7588  Vol.:   41.842  Label: V(F6)
Basin    5  Pop.:  2.6866  Vol.:   40.412  Label: V(F2)
Basin    6  Pop.:  2.6868  Vol.:   39.994  Label: V(F6)
Basin    7  Pop.:  1.1917  Vol.:    1.520  Label: V(F2,Be5)
Basin    8  Pop.:  1.1916  Vol.:    1.520  Label: V(Be5,F6)
Basin    9  Pop.:  2.1478  Vol.:    0.025  Label: C(F7)
Basin   10  Pop.:  2.1436  Vol.:    0.025  Label: C(F8)
Basin   11  Pop.:  0.1401  Vol.:    5.491  Label: V(F8)
Basin   12  Pop.:  2.6661  Vol.:   61.656  Label: V(F8)
Basin   13  Pop.:  0.1405  Vol.:    5.506  Label: V(F8)
Basin   14  Pop.:  1.2711  Vol.:    1.617  Label: V(Be5,F8)
Basin   15  Pop.:  0.0638  Vol.:    3.190  Label: V(F7)
Basin   16  Pop.:  0.0638  Vol.:    3.171  Label: V(F7)
Basin   17  Pop.:  2.8711  Vol.:   64.571  Label: V(F7)
Basin   18  Pop.:  1.2669  Vol.:    1.601  Label: V(Be5,F7)
Basin   19  Pop.:  2.0565  Vol.:    0.651  Label: C(Be5)
Basin   20  Pop.:  2.8704  Vol.:   64.522  Label: V(F3)
Basin   21  Pop.:  2.6648  Vol.:   61.330  Label: V(F4)
Basin   22  Pop.:  1.1918  Vol.:    1.520  Label: V(Be1,F2)
Basin   23  Pop.:  1.1917  Vol.:    1.520  Label: V(Be1,F6)
Basin   24  Pop.:  1.2711  Vol.:    1.616  Label: V(Be1,F4)
Basin   25  Pop.:  1.2669  Vol.:    1.601  Label: V(Be1,F3)
Basin   26  Pop.:  2.1513  Vol.:    0.025  Label: C(F2)
Basin   27  Pop.:  2.1513  Vol.:    0.025  Label: C(F6)
Basin   28  Pop.:  0.1406  Vol.:    5.561  Label: V(F4)
Basin   29  Pop.:  0.1406  Vol.:    5.509  Label: V(F4)
Basin   30  Pop.:  0.0638  Vol.:    3.175  Label: V(F3)
Basin   31  Pop.:  0.0640  Vol.:    3.168  Label: V(F3)
Basin   32  Pop.:  3.5685  Vol.:  138.659  Label: V(F3)
Basin   33  Pop.:  3.6200  Vol.:  132.383  Label: V(F4)
Basin   34  Pop.:  2.1478  Vol.:    0.025  Label: C(F3)
Basin   35  Pop.: 19.0373  Vol.:    0.651  Label: C(Be1)
Basin   36  Pop.:  2.1436  Vol.:    0.025  Label: C(F4)

Sum of core basin populations:        33.9792
Sum of valence basin populations:     46.9992
Sum of all basin populations:         80.9785

Note that the sum of valence basin populations is nearly identical to that found in Be2F6 vacuum wfn file on the same quality grid (lunatic), which is 46.9920. Sum of core basin populations on the vacuum wfn file is 17.0051. The error appears to come entirely from C(Be1) with estimated 19.0373 electrons.

The .wfn file for this calculation is Be2F6_dianion_water.wfn, posted in the google drive link above.

What could be causing the issue here?

It is fully possible to use implicit solvation model when generating wavefunction files.

May I still ask is it feasible to do this analysis (17 1 9 4 12) when implicit solvent was used via SCRF(SMD) command in Gaussian16 when generating the wfn file?

I am trying to analyze ELF on a system [M2X6]2- M = Be, X = F, Cl, Br in gas phase and water.

Structures have been optimized in gas phase and water, respectively. WFN file was generated along with the SP calculation of the minima structures (Gaussian16) with route section "M062X/aug-cc-pvdz SCF(VeryTight) Integral(SuperFine) output=wfn" + "SCRF(SMD, solvent=water)" if water in the title name.

Multiwfn 3.8 dev binary build for Linux. The command sequence i am using is: 17 1 9 (options 1-4) 12

Problem 1 (gas phase, no solvent!): For X = Br, low and medium quality grids produce too low total populations, high quality results in hundreds of electrons more than it should. Lunatic quality results in segmentation fault during search for attractors. Note, for X = F, Cl, high and lunatic quality produce very good result.

Problem 2 (solvent present): This i am not sure if it has to do with grid quality or rather artefacts of the SCRF(SMD) generated WFN. Be2F6 in water integrates to 80 electrons.

The wawefunction files are too large to upload to the forum. I am sharing a google drive link with relevant .wfn files, .xyz structures of the minima and .log files of mentioned multiwfn runs (multiwfn title.wfn | tee title.log).

If i may use the chance to ask how is ELF gradient calculated, are the derivatives analytical?

https://drive.google.com/file/d/1PI1xnQ … sp=sharing

Thank you very much for your time!