<div dir="ltr">Hello CP2K users<div> </div><div>I wanted to understand what is the effect of adding +U correction to the energies of calculations without any U. For example, I have a Cu atom for which I am interested in finding the DFT and DFT+U energy. I have provided the input file below. </div><div> </div><div>In an attempt to see what U does, I looked at the Fermi energies of the two calculations. When I do an energy run without any U, I get the Fermi energy to be -0.163318 Ha while upon inclusion of U=5.0 eV, I get the Fermi energy to be -0.16497 Ha. The difference (Energy with U - Energy without U) is -0.05 eV. This means that adding U shifts the energy levels of the electronic states to more negative values. I tried the same calculation with VASP and I get the same difference in fermi energies to be +0.12 eV. I was thinking that adding U would shift the fermi energy to more positive values compared to when no U is applied. Is that correct? </div><div> </div><div>Secondly, with respect to the DFT energy of a Cu atom, in CP2K, the effect of U is negligible. Adding U =5.0 eV gives a "DFT+U energy: 0.00000001917427", which is almost zero. However, Using VASP, when U=5.0 eV was turned on, the DFT energy of Cu atom becomes more positive by +1.2 eV compared to calculation without U. Could someone help me with what is going on? or if there are some changes to the input file that may fix this issue of almost zero DFT+U energy?</div><div> </div><div>On a different note, I was thinking that since Cu atom has all the d electrons filled and paired up, application of U to these d electrons would not change the electronic occupations and hence would not change the DFT+U energy. But from VASP it did look like the electronic occupations were not changed much by inclusion of U but the energies did change considerable. I was confused what is going on. </div><div> </div><div>Finally, I used PLUS_U_METHOD LOWDIN since MULLIKEN/MULLIKEN_CHARGES gave me the following warnings. Does this change the above things by any chance? I don't think so. But if it does, please let me know any suggestions to get rid of the warning. </div><div> *** 13:28:53 WARNING in dft_plus_u:mulliken_charges :: DFT+U energy *** *** contibution is negative possibly due to unphysical Mulliken charges. *** *** Check your input, if this warning persists or try a different method! *** Input file: &FORCE_EVAL METHOD Quickstep &DFT PLUS_U_METHOD LOWDIN UKS BASIS_SET_FILE_NAME /home/siyemperumal/GTH_BASIS_SETS_5-12-10 POTENTIAL_FILE_NAME /home/siyemperumal/GTH_POTENTIALS_5-12-10 WFN_RESTART_FILE_NAME mol-RESTART.wfn &MGRID CUTOFF 300 &END MGRID &QS WF_INTERPOLATION ASPC EXTRAPOLATION_ORDER 3 &END QS &SCF EPS_SCF 1.E-6 SCF_GUESS RESTART MAX_SCF 500 &DIAGONALIZATION ALGORITHM STANDARD &END DIAGONALIZATION ADDED_MOS 60 &SMEAR ON METHOD FERMI_DIRAC ELECTRONIC_TEMPERATURE [K] 300 &END SMEAR &MIXING METHOD DIRECT_P_MIXING &END MIXING &END SCF &XC &XC_FUNCTIONAL PBE &END XC_FUNCTIONAL &VDW_POTENTIAL DISPERSION_FUNCTIONAL PAIR_POTENTIAL &PAIR_POTENTIAL TYPE DFTD3(BJ) PARAMETER_FILE_NAME /home/siyemperumal/Research/cp2k/package/cp2k/data/dftd3.dat REFERENCE_FUNCTIONAL PBE &PRINT_DFTD MEDIUM &END PRINT_DFTD &END PAIR_POTENTIAL &END VDW_POTENTIAL &END XC &PRINT &MO EIGENVALUES OCCUPATION_NUMBERS &EACH QS_SCF 0 &END EACH &END MO &END PRINT &END DFT &SUBSYS &CELL ABC 12.00 13.00 14.00 PERIODIC NONE &END CELL &COORD Cu 0.0000153980 0.0000010425 0.0006891492 &END COORD &KIND Cu BASIS_SET DZVP-MOLOPT-SR-GTH POTENTIAL GTH-PBE-q11#I remove the following DFT calculation. I also tried ramping and other associated keywords but with no success. &DFT_PLUS_U L 2 U_MINUS_J [eV] 5.00 &END DFT_PLUS_U &END SUBSYS &END FORCE_EVAL&GLOBAL PROJECT mol RUN_TYPE ENERGY PRINT_LEVEL LOW &END GLOBAL </div> </div>