[CP2K-user] [CP2K:21180] Re: Issue with excitation energies (TDDFT) when using the wB97XD functional

Raphaël Rullan raphael.rullan at gmail.com
Thu Feb 20 09:45:32 UTC 2025


Dear CP2K users, 
Sorry for bothering you again with this topic but I did not find any 
answers yet despite the many attempts. Does anyone have an idea of what 
could be the problem? 

I also would like to raise another issue I encountered while running 
RKS_TRIPLETS calculations. For PBE and PBE0 I have no issue but as soon as 
I try B3LYP or CAM-B3LYP it stopped with a scary error message (presented 
below). Does anyone encountered this issue and maybe have an idea about how 
to deal with it ? I don't think that the memory issue comes from my 
computer.
Thank you very much, 
Best regards,
Raphael Rullan

==== backtrace (tid: 253750) ====

 0 0x0000000000013140 __funlockfile()  :0

 1 0x0000000002e7078c __xc_MOD_xc_calc_2nd_deriv_analytical._omp_fn.90()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/xc.F90:2766

 2 0x0000000000015076 GOMP_parallel()  
/applis/PSMN/debian11/Lake/build/GCCcore/12.3.0/system-system/gcc-12.3.0/stage3_obj/x86_64-pc-linux-gnu/libgomp/../../../libgomp/parallel.c:178

 3 0x0000000000015076 GOMP_parallel_end()  
/applis/PSMN/debian11/Lake/build/GCCcore/12.3.0/system-system/gcc-12.3.0/stage3_obj/x86_64-pc-linux-gnu/libgomp/../../../libgomp/parallel.c:140

 4 0x0000000000015076 GOMP_parallel()  
/applis/PSMN/debian11/Lake/build/GCCcore/12.3.0/system-system/gcc-12.3.0/stage3_obj/x86_64-pc-linux-gnu/libgomp/../../../libgomp/parallel.c:179

 5 0x0000000002ea830d __xc_MOD_xc_calc_2nd_deriv_analytical()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/xc.F90:2766

 6 0x000000000274b877 
__qs_tddfpt2_operators_MOD_tddfpt_apply_xc_analytic()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_tddfpt2_operators.F90:378

 7 0x000000000274d82a __qs_tddfpt2_operators_MOD_tddfpt_apply_xc()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_tddfpt2_operators.F90:248

 8 0x0000000002615a53 __qs_tddfpt2_fhxc_MOD_fhxc_kernel()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_tddfpt2_fhxc.F90:261

 9 0x00000000024a9f4e 
__qs_tddfpt2_eigensolver_MOD_tddfpt_davidson_solver()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_tddfpt2_eigensolver.F90:378

10 0x00000000024a9f4e 
__qs_tddfpt2_eigensolver_MOD_tddfpt_davidson_solver()  
/Xnfs/chimie/debian11/cp2k/2023.2/src/qs_tddfpt2_eigensolver.F:769

11 0x00000000021b3a80 __qs_tddfpt2_methods_MOD_tddfpt_energies()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_tddfpt2_methods.F90:952

12 0x00000000021b7ea2 __qs_tddfpt2_methods_MOD_tddfpt()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_tddfpt2_methods.F90:339

13 0x00000000016748b3 __qs_energy_utils_MOD_qs_energies_properties()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_energy_utils.F90:157

14 0x0000000000d78a53 __qs_energy_MOD_qs_energies()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/qs_energy.F90:136

15 0x0000000000bc66ff 
__force_env_methods_MOD_force_env_calc_energy_force()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/force_env_methods.F90:256

16 0x0000000000803cfb __cp2k_runs_MOD_cp2k_run.constprop.0()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/cp2k_runs.F90:355

17 0x0000000000806793 __cp2k_runs_MOD_run_input()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/cp2k_runs.F90:997

18 0x00000000007f9023 MAIN__()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/cp2k.F90:379

19 0x0000000000491cad main()  
/Xnfs/chimie/debian11/cp2k/2023.2/obj/local/psmp/cp2k.F90:44

20 0x0000000000023d7a __libc_start_main()  ./csu/../csu/libc-start.c:308

21 0x00000000007f750a _start()  ???:0

=================================

==== backtrace (tid: 253743) ====


Program received signal SIGSEGV: Segmentation fault - invalid memory 
reference.

Le lundi 13 janvier 2025 à 18:15:16 UTC+1, Raphaël Rullan a écrit :

> Dear CP2K users,
> Sorry for bothering you again. I observed a particularly strange issue 
> while running a TDDFT calculation. The calculation seems to be running just 
> fine,  the SCF part converged and the energies of the orbitals seem fine. 
> The TDDFT part start, the guess seems consistent with the HOMO-LUMO gap and 
> it starts to converge. At some point a new excitation appears with a 
> negative energy (see below and .out). I don't understand why, and how I 
> could fix this. I guess maybe the GS wavefunction is not fully converged 
> but the code says so. Any idea ?
> The example below is from a TDDFT calculation using the wB97-XD functional 
> with the 2023 CP2K release.  However, I also observed this issue  with the 
> PBE0 functional with a different version of CP2K (2022).
>
> State    Exc. energy (eV)      Convergence (eV)
>
>         1       2.6610598            -3.1548E-01
>
>         2       2.6610618            -3.1548E-01
>
>         3       2.6610647            -3.1548E-01
>
>         4       3.9977385            -3.6060E-01
>
>         5       4.8783993            -5.6683E-01
>
>         6       4.8784003            -5.6683E-01
>
>         7       5.0410401            -5.2693E-01
>
>         8       5.0410451            -5.2693E-01
>
>         9       5.0410482            -5.2693E-01
>
>        10       5.4661866            -3.0007E-01
>
>
>              2         10573.8          2.0831E-02                      0
>
>
>     State    Exc. energy (eV)      Convergence (eV)
>
>         1       2.6372645            -2.3795E-02
>
>         2       2.6376604            -2.3401E-02
>
>         3       2.6378627            -2.3202E-02
>
>         4       3.9549216            -4.2817E-02
>
>         5       4.6556179            -2.2278E-01
>
>         6       4.6556197            -2.2278E-01
>
>         7       4.9364090            -1.0463E-01
>
>         8       4.9401741            -1.0087E-01
>
>         9       4.9418617            -9.9187E-02
>
>        10       5.3915938            -7.4593E-02
>
>
>              3          9342.6          8.1871E-03                      0
>
>
>     State    Exc. energy (eV)      Convergence (eV)
>
>         1       2.6348592            -2.4052E-03
>
>         2       2.6362756            -1.3847E-03
>
>         3       2.6365731            -1.2896E-03
>
>         4       3.9509578            -3.9639E-03
>
>         5       4.5793122            -7.6306E-02
>
>         6       4.5793141            -7.6306E-02
>
>         7       4.9300251            -6.3839E-03
>
>         8       4.9328265            -7.3477E-03
>
>         9       4.9344891            -7.3726E-03
>
>        10       5.3743071            -1.7287E-02
>
>
>              4          9335.0          2.8042E-03                      0
>
>
>     State    Exc. energy (eV)      Convergence (eV)
>
>         1     -68.5095683            -7.1144E+01
>
>         2       2.6342572            -2.0185E-03
>
>         3       2.6345047            -2.0684E-03
>
>         4       2.6362695            -1.3147E+00
>
>         5       3.9507303            -6.2858E-01
>
>         6       4.5663465            -1.2968E-02
>
>         7       4.5663508            -3.6367E-01
>
>         8       4.9201774            -1.2649E-02
>
>         9       4.9229758            -1.1513E-02
>
>        10       4.9321820            -4.4213E-01
>
>
> Thank you very much,
> Have a good day,
> Best regards
> Raphael Rullan
>

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