<div> </div><div> </div>Dear Emma,<div> </div><div>Both Mg and Na have quite hard functions in the basis set, it might be that the cutoff of 600 Ry is not sufficient.</div><div>Have you checked whether the electronic structure is OK (e.g. energy gap) ? </div><div>Often the localisation algorithm shows convergence problems when there are intrinsically very delocalised states (see metals).</div><div>Maybe this is not the problem though. Are the Wannier centres after localisation at the expected positions ? </div><div> </div><div>Regards</div><div>Marcella</div><div> </div><div> </div><div> </div><div class="gmail_quote"><div dir="auto" class="gmail_attr">On Friday, October 20, 2023 at 11:09:48 AM UTC+2 Emma Rossi wrote: </div><blockquote class="gmail_quote" style="margin: 0 0 0 0.8ex; border-left: 1px solid rgb(204, 204, 204); padding-left: 1ex;">Dear developers and CP2K users, <div>I'm running AIMD simulations and computing the total dipole moment of a 15 A cubic box (Berry phase approach) containing water molecules, a phosphate chain (-4) and a divalent cation, either Zn2+ or Mg2+. </div><div>For Mg2+, the convergence of the MOs localization process at each step is tremendously slower (one/two order of magnitude) compared to the box with Zn2+. I cannot figure out the reason of such behaviour. I use the default setting for the LOCALIZE section, which employs the JACOBI method.</div> <div>The -2 net charge of the system is counterbalanced by uniform background. 600 Ry cutoff for the auxiliary PW expansion of the electron density (500 or 400 Ry are used in the literature for Zn2+ and Mg2+ respectively) and BLYP XC are used. DZVP-MOLOPT-SR-GTH-q10 and DZVP-MOLOPT-SR-GTH-q12 are used for Mg2+ and Zn2+ respectively. </div><div> </div>I observe a similar slowdown of the MOs localization speed when I use Na+ atoms to counterbalance the -2 charge of the system containing Zn2+. Here a typical input file follows. &GLOBAL PRINT_LEVEL LOW PROJECT_NAME MD RUN_TYPE MD &END GLOBAL &MOTION &MD ENSEMBLE NVT STEPS 100 TIMESTEP 0.5 TEMPERATURE 3.0000000000000000E+02 TEMP_TOL 5.0000000000000000E+01 &THERMOSTAT TYPE CSVR &CSVR TIMECON 2.4999999999999996E+01 &END CSVR &END THERMOSTAT &END MD &END MOTION &FORCE_EVAL METHOD QS &DFT BASIS_SET_FILE_NAME BASIS_MOLOPT POTENTIAL_FILE_NAME GTH_POTENTIALS CHARGE -2 &SCF MAX_SCF 100 EPS_SCF 4.9999999999999998E-07 SCF_GUESS RESTART &OT T MINIMIZER DIIS PRECONDITIONER FULL_KINETIC &END OT &END SCF &MGRID CUTOFF 6.0000000000000000E+02 &END MGRID &XC DENSITY_CUTOFF 1.0000000000000000E-10 GRADIENT_CUTOFF 1.0000000000000000E-10 TAU_CUTOFF 1.0000000000000000E-10 &XC_GRID XC_SMOOTH_RHO NN10 XC_DERIV SPLINE2_SMOOTH &END XC_GRID &XC_FUNCTIONAL NO_SHORTCUT &BECKE88 T &END BECKE88 &LYP T &END LYP &END XC_FUNCTIONAL &VDW_POTENTIAL &PAIR_POTENTIAL R_CUTOFF 8.0000000000000000E+00 TYPE DFTD3(BJ) PARAMETER_FILE_NAME dftd3.dat REFERENCE_FUNCTIONAL BLYP EPS_CN 1.0000000000000000E-02 CALCULATE_C9_TERM T REFERENCE_C9_TERM T LONG_RANGE_CORRECTION T &END PAIR_POTENTIAL &END VDW_POTENTIAL &END XC &LOCALIZE T &PRINT &TOTAL_DIPOLE ON FILENAME =totdipole PERIODIC T &EACH MD 1 &END EACH &END TOTAL_DIPOLE &END PRINT &END LOCALIZE &END DFT &SUBSYS &CELL A 1.5460000000000001E+01 0.0000000000000000E+00 0.0000000000000000E+00 B 0.0000000000000000E+00 1.5460000000000001E+01 0.0000000000000000E+00 C 0.0000000000000000E+00 0.0000000000000000E+00 1.5460000000000001E+01 MULTIPLE_UNIT_CELL 1 1 1 &END CELL &KIND O BASIS_SET DZVP-MOLOPT-GTH-q6 POTENTIAL GTH-BLYP-q6 &END KIND &KIND H BASIS_SET DZVP-MOLOPT-GTH-q1 POTENTIAL GTH-BLYP-q1 &END KIND &KIND C BASIS_SET DZVP-MOLOPT-GTH-q4 POTENTIAL GTH-BLYP-q4 &END KIND &KIND P BASIS_SET DZVP-MOLOPT-GTH-q5 POTENTIAL GTH-BLYP-q5 &END KIND &KIND Na BASIS_SET DZVP-MOLOPT-SR-GTH-q9 POTENTIAL GTH-BLYP-q9 &END KIND &KIND Mg BASIS_SET DZVP-MOLOPT-SR-GTH-q10 POTENTIAL GTH-BLYP-q10 &END KIND &TOPOLOGY NUMBER_OF_ATOMS 384 MULTIPLE_UNIT_CELL 1 1 1 &END TOPOLOGY &END SUBSYS &END FORCE_EVAL Here a piece of the file.out concerning the localization is reported ENSEMBLE TYPE = NVT STEP NUMBER = 48740 TIME [fs] = 24370.000000 CONSERVED QUANTITY [hartree] = -0.234908827385E+04 INSTANTANEOUS AVERAGES CPU TIME [s] = 220.24 29.11 ENERGY DRIFT PER ATOM [K] = -0.274167730955E+04 -0.106732023761E+04 POTENTIAL ENERGY[hartree] = -0.235022491736E+04 -0.234811418791E+04 KINETIC ENERGY [hartree] = 0.530388799833E+00 0.547854613121E+00 TEMPERATURE [K] = 291.529 301.129 *************************** Number of electrons: 1070 Number of occupied orbitals: 535 Number of molecular orbitals: 535 Number of orbital functions: 3012 Number of independent orbital functions: 3012 Extrapolation method: ASPC SCF WAVEFUNCTION OPTIMIZATION ----------------------------------- OT --------------------------------------- Minimizer : DIIS : direct inversion in the iterative subspace using 7 DIIS vectors safer DIIS on Preconditioner : FULL_KINETIC : inversion of T + eS Precond_solver : DEFAULT stepsize : 0.15000000 energy_gap : 0.20000000 eps_taylor : 0.10000E-15 max_taylor : 4 ----------------------------------- OT --------------------------------------- Step Update method Time Convergence Total energy Change ------------------------------------------------------------------------------ 1 OT DIIS 0.15E+00 4.9 0.00001365 -2350.2265786077 -2.35E+03 2 OT DIIS 0.15E+00 7.0 0.00000785 -2350.2266129356 -3.43E-05 3 OT DIIS 0.15E+00 7.0 0.00000667 -2350.2266281036 -1.52E-05 4 OT DIIS 0.15E+00 7.0 0.00000316 -2350.2266318502 -3.75E-06 5 OT DIIS 0.15E+00 7.1 0.00000285 -2350.2266340790 -2.23E-06 6 OT DIIS 0.15E+00 7.0 0.00000168 -2350.2266355491 -1.47E-06 7 OT DIIS 0.15E+00 7.1 0.00000158 -2350.2266365271 -9.78E-07 8 OT DIIS 0.15E+00 7.0 0.00000079 -2350.2266370647 -5.38E-07 9 OT DIIS 0.15E+00 7.1 0.00000054 -2350.2266374235 -3.59E-07 10 OT DIIS 0.15E+00 7.0 0.00000041 -2350.2266374897 -6.63E-08 * SCF run converged in 10 steps * Electronic density on regular grids: -1069.9999984366 0.0000015634 Core density on regular grids: 1067.9999999649 -0.0000000351 Total charge density on r-space grids: -1.9999984716 Total charge density g-space grids: -1.9999984716 Overlap energy of the core charge distribution: 0.00000352123302 Self energy of the core charge distribution: -6058.29367128599642 Core Hamiltonian energy: 1758.83041225385932 Hartree energy: 2514.80853697306702 Exchange-correlation energy: -565.57191895188691 Total energy: -2350.22663748972354 LOCALIZE| The spread relative to a set of orbitals is computed LOCALIZE| Orbitals to be localized: All orbitals LOCALIZE| If fractional occupation, fully occupied MOs are those within occupation tolerance of 0.00000001 LOCALIZE| Spread defined by the Berry phase operator LOCALIZE| Optimal unitary transformation generated by Jacobi algorithm Eigenvalues of the occupied subspace spin 1 --------------------------------------------- -2.77340522 -1.55519360 -1.55401616 -1.55312686 -0.84401306 -0.81554322 -0.80702571 -0.80237237 -0.80085752 -0.79902548 -0.79112340 -0.79067760 -0.78889214 -0.78844561 -0.78745096 -0.78661985 -0.78594483 -0.78398619 -0.78359896 -0.78223867 -0.78202387 -0.78089859 -0.77900446 -0.77831838 -0.77761721 -0.77700210 -0.77677871 -0.77654095 -0.77610461 -0.77529141 -0.77482833 -0.77403370 [.......] -0.09177880 -0.09168157 -0.09118981 -0.09045276 -0.09027640 -0.08911508 -0.08871380 -0.08817562 -0.08660485 -0.08624312 -0.08399649 -0.08220911 -0.07894380 -0.07429071 -0.06779908 Fermi Energy [eV] : -1.844907 LOCALIZATION| Computing localization properties for OCCUPIED ORBITALS. Spin: 1 Spread Functional sum_in -w_i ln(|z_in|^2) sum_in w_i(1-|z_in|^2) Initial Spread (Berry) : 203183.2008851338 34522.<a href="tel:(934)%20645-3651" value="+19346453651" target="_blank" rel="nofollow">9346453651</a> Localization by iterative distributed Jacobi rotation Iteration Functional Tolerance Time 100 1035.1444747551 0.7611E-01 0.145 200 1035.1439265702 0.2374E-01 0.145 300 1035.1438285431 0.2086E-01 0.145 400 1035.1437772042 0.1457E-01 0.155 500 1035.1437553092 0.8452E-02 0.146 600 1035.1437479886 0.4565E-02 0.156 700 1035.1437457665 0.2413E-02 0.144 800 1035.1437451192 0.1268E-02 0.155 900 1035.1437449348 0.6661E-03 0.155 1000 1035.1437448830 0.3497E-03 0.156 1100 1035.1437448685 0.1836E-03 0.169 Localization for spin 1 converged in 1195 iterations Spread Functional sum_in -w_i ln(|z_in|^2) sum_in w_i(1-|z_in|^2) Total Spread (Berry) : 1051.<a href="tel:(831)%20528-3360" value="+18315283360" target="_blank" rel="nofollow">8315283360</a> 1035.1437448646 <div> </div><div>To check the role of the localization method in such problem, I ran two single point calculations, the first using the JACOBI method and the second using the CRAZY method to compute the total dipole. The latter makes the process even slower. </div><div> </div><div>I would be very grateful if any of you could give me any insight. </div> Best regards, Emma Rossi</blockquote></div> -- You received this message because you are subscribed to the Google Groups "cp2k" group. To unsubscribe from this group and stop receiving emails from it, send an email to <a href="mailto:cp2k+unsubscribe@googlegroups.com">cp2k+unsubscribe@googlegroups.com</a>. To view this discussion on the web visit <a href="https://groups.google.com/d/msgid/cp2k/a4de3df0-0d85-44ec-8b5f-138082684895n%40googlegroups.com?utm_medium=email&utm_source=footer">https://groups.google.com/d/msgid/cp2k/a4de3df0-0d85-44ec-8b5f-138082684895n%40googlegroups.com</a>.