[CP2K-user] [CP2K:21039] Issue with excitation energies (TDDFT) when using the wB97XD functional

[Raphaël Rullan]

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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