[CP2K-user] [CP2K:18094] fluorescence wavelength by CP2K

[Victor Volkov]

*Dear developers:*
good morning/evening.
Using pyrimidine, I try to understand how to compute 0'-0 fluorescence 
energy (wavelength).

*In gaussian, this relatively* well-established series of three 
calculations:
1) B3LYP/6-31+G(d,p) Opt 
2) B3LYP/6-31+G(d,p) TD=(nstates=xx) 
3) B3LYP/6-31+G(d,p) Opt TD=(nstates=xx,root=state_of_interest) 
Emission energy is the difference Eex - Eexgr, where
Eex is the energy of the excited state: print in the string "TD-KS".
Eexgr is the ground state energy of the excited state geometry: print for 
the string "HF=-". 

*Here, I attach current CP2K results for pyrimidine *structural optimization
in the first excited state, while accounting the excitation set to include 
three states.

Upon every optimization cycle, the output file reports four energies, for 
example:
1) Total energy:                                               
-45.00011553431995
 !--------------------------- Excited State Energy 
----------------------------!
2) Excitation Energy [Hartree]                                     
0.1408310694
3) Total Energy [Hartree]                                           
-44.8592844650
4)  ENERGY| Total FORCE_EVAL ( QS ) energy [a.u.]:   -44.859271658539249

*Would you comment what are these?*
Why there are three TOTALS?

*Next, in the input file I instruct*
&MOTION
  &GEO_OPT
    MAX_DR    1.0E-03
    MAX_FORCE 1.0E-03
    RMS_DR    1.0E-03    
    RMS_FORCE 1.0E-03
    OPTIMIZER CG
but, it seems, the output file does not report on the convergence criteria.
*Does TDDFPT require additional instruction that such data would be printed*
*or this is out of the scope of the current package?*

*Finally, I see that upon the start:*
-                            Excitation analysis                           
   -
 -------------------------------------------------------------------------------
        State             Occupied              Virtual             
Excitation
        number             orbital              orbital             
amplitude
 -------------------------------------------------------------------------------
             1   3.83221 eV
                                15                   16               
0.995900
                                14                   17             
 -0.072640
             2   4.07218 eV
                                15                   17               
0.989483
                                14                   16             
 -0.140638
             3   5.17410 eV
                                14                   16             
 -0.982529
                                15                   17             
 -0.137943
                                15                   18               
0.080624
                                13                   16             
 -0.068511
 -------------------------------------------------------------------------------


*while later, upon optimization:*
-                            Excitation analysis                           
   -
 -------------------------------------------------------------------------------
        State             Occupied              Virtual             
Excitation
        number             orbital              orbital             
amplitude
 -------------------------------------------------------------------------------
             1   3.01565 eV
                                15                   16             
 -0.997677
             2   3.59856 eV
                                15                   17               
0.989952
                                14                   16             
 -0.137983
             3   4.63370 eV
                                14                   16             
 -0.985780
                                15                   17             
 -0.135202
                                15                   18             
 -0.077828
 -------------------------------------------------------------------------------

*Since the latter excitation energy  of 3.01565 eV is significantly lower 
than the initial one of 3.83221 eV, should the difference of about 0.8eV 
correspond to the Stokes shift,*
*and the 3.01565 eV would be the desired 0'-0 fluorescence energy?*

Thank you.
I hope/wish the users would find my questions valuable.

With best wishes.
Victor 

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