Dear Nick, the mismatch comes from interpreting the GAPW soft density as a valence-only density. Your log already accounts for approximately 102 electrons in the complete electronic density, so it does not indicate an extra electron or an electron-counting error in the SCF. In your all-electron calculation, rho_soft + rho1_hard - rho1_soft is the complete density, including core and valence electrons. It should therefore integrate to 102 electrons, not 76. The GAPW hard/soft decomposition is not a chemical core/valence partition. NGAUSS is used by XRD_INTERFACE and does not remove core electrons from the SOFT_DENSITY cube. For DDEC6, I recommend exporting the Gaussian-orbital wavefunction in WFX format rather than supplying the soft-density cube. Chargemol can then evaluate and partition the complete electronic density using its own density treatment. For an all-electron WFX file, do not declare the 26 core electrons as missing electrons, since they are already included. Rescaling the soft cube to 76 electrons would not restore the missing density shape. CP2K already has a CHARGEMOL/WFX exporter, but it currently rejects OT wavefunctions. I have opened a PR to enable OT export, including UKS and ADMM, using private copies of the occupied orbitals without changing the SCF state: https://github.com/cp2k/cp2k/pull/6276 With a build containing this patch, you can add the following under FORCE_EVAL/DFT/PRINT to export every tenth MD step: &CHARGEMOL ON FILENAME chargemol &EACH MD 10 &END EACH &END CHARGEMOL The PR is not merged yet. Without the patch, diagonalization-based SCF remains an alternative for WFX export. I tested the export with all-electron OT calculations, including UKS and ADMM. For a simplified PBE/6-31G* calculation using your 24-atom molecular geometry, Chargemol accounted for all 102 electrons and completed DDEC6 normally. This validates the export and electron accounting, not the numerical charges of your original hybrid QM/MM trajectory, which I have not reproduced. For the cutoff question, WFX avoids the cube representation of sharp core-density peaks, but does not replace convergence tests of the underlying calculation. Check energies, forces and the charges of interest against CUTOFF, REL_CUTOFF and the GAPW atomic grids. Finally, since the gold slab is classical MM, this analysis covers the QM ion pair only. It cannot assign DDEC6 charges to the gold atoms or describe electron transfer involving metallic electronic states that are absent from the model. Best regards, Thomas <div class="gmail_quote"><div dir="auto" class="gmail_attr">On Wednesday, May 7, 2025 at 7:48:17 PM UTC+2 Nicholas Laws wrote: </div><blockquote class="gmail_quote" style="margin: 0 0 0 0.8ex; border-left: 1px solid rgb(204, 204, 204); padding-left: 1ex;"><span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Hi CP2K Community,<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">I am trying to obtain time-dependent <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">DDEC6<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> charges for a mixed <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">QM/MM<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> simulation in which an <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">EMI-BF4 ion pair (76 valence e, 26 core e)<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> collides with a gold slab at various kinetic energies. The QM region is treated with <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">ωB97X-V/aug-cc-pVTZ<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> and <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">all-electron<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> potentials in <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">GAPW<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">. During production (input ESC<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-style:italic;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">ollision.inp<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">, attached) I print a cube with:<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">&PRINT<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> &E_DENSITY_CUBE<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> DENSITY_INCLUDE SOFT_DENSITY<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> NGAUSS 0<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> STRIDE 1 1 1<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> FILENAME valence_density<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> &END<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">&END<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">and a 5-level PW grid of:<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">&MGRID<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> NGRIDS 5<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> CUTOFF 800<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> REL_CUTOFF 80<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline"> COMMENSURATE .TRUE.<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">&END<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">The log shows:<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Electronic density on regular grids: -76.<a href="tel:(765)%20826-6487" value="+17658266487" target="_blank" rel="nofollow">7658266487</a> 25.2341733513<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Core density on regular grids: 102.0000000000 -0.0000000000<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Hard and soft densities (Lebedev): -694.5370264067 -669.<a href="tel:(302)%20856-6617" value="+13028566617" target="_blank" rel="nofollow">3028566617</a><span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Total Rho_soft + Rho1_hard - Rho1_soft -101.9999963937<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Total charge density (r-space): 0.0000036063<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Total Rho_soft + Rho0_soft (g-space): 0.0000033449 <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Overlap energy of the core charge distribution: 0.00002215241243<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Self energy of the core charge distribution: -720.29674329623936<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Core Hamiltonian energy: -75.86850888340894<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Hartree energy: 209.46847518535864<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Exchange-correlation energy: -26.02788481604846<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Hartree-Fock Exchange energy: -28.87249823090302<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Dispersion energy: 0.25782644744755<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">so the cube integrates to <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">≈77 e <span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">instead of the expected 76 e. Chargemol therefore exits with<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">ncore = 26.0000<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">nvalence = 76.0000<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">pixelvolume = 1.3079E-03<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-weight:700;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">numerically integrated valence density = 7.6767E+01<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">sum_valence_occupancy_correction = 0.0000E+00<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">checkme = 7.6659E-01<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">The electrons are not properly accounted for. Either the grid in your electron density input file is too coarse, you have specified the incorrect net charge in the chargemol_job.m file, or the number of core electrons for each atom has not been set up correctly.<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Program will terminate.<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">My questions are:<ol style="margin-top:0px;margin-bottom:0px"><li dir="ltr" style="list-style-type:decimal;font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline;white-space:pre">Is there any keyword combination in GAPW that prints only the valence density (ρ_soft + ρ₁,hard − ρ₁,soft) so the integral matches 76 e, or must I run a GPW single-point for every MD frame?</li><li dir="ltr" style="list-style-type:decimal;font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline;white-space:pre">Is there a published benchmark for the PW cutoff required to converge ωB97X-V + aug-cc-pVTZ?</li></ol><span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Any hints, keywords, code pointers, or literature would be greatly appreciated!<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Many thanks in advance,<span style="font-size:11pt;font-family:Arial,sans-serif;color:rgb(0,0,0);background-color:transparent;font-variant-numeric:normal;font-variant-east-asian:normal;font-variant-alternates:normal;vertical-align:baseline">Nick</blockquote></div> -- You received this message because you are subscribed to the Google Groups "cp2k" group. 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