[DFTB-Plus-User] The unreasonable results of transition dipole moment between ground state and excited state by DFTB+

Chencheng Fan s8chfann at stud.uni-saarland.de
Sun Jul 11 14:43:41 CEST 2021


Thank you Sharma for your suggestions. I have tried the calculations again with SCC tolerance as 1e-5 for both ground state and excited state calculations. However, the “TDP.DAT” doesn’t change much and the magnitude is still quite large as I enclosed below.

Best regards
Chencheng

“TDP.DAT" with SCC tolerance 1e-5 :
     #     w [eV]  Transition dipole (x,y,z) [Debye]

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

     1      2.152  -3.543706E+07-6.239148E+07 7.798202E+06
     2      2.356  -1.202240E+08-2.959260E+08 4.570323E+07
     3      2.592   6.280149E+06 1.136275E+07-3.032020E+06
     4      2.706   4.824718E+06 8.208777E+06-1.645247E+06
     5      3.670  -1.737782E+06-2.740595E+05 1.751733E+05
     6      3.700   1.374672E+06-1.570435E+05-1.005007E+05
     7      3.804  -8.318873E+05 1.714250E+05 2.898974E+05
     8      4.099   5.207557E+05-2.097614E+04-2.789934E+05
     9      4.135  -1.061940E+05-1.719483E+05 1.896487E+05
    10      4.203  -7.995673E+05 2.293393E+04 1.205273E+05
    11      4.240   4.637786E+05 1.273760E+05-3.698055E+04
    12      4.305   2.873024E+06-1.649365E+05-5.466033E+05
    13      4.647   6.482171E+04 8.919392E+03-1.672855E+04
    14      4.763  -1.159784E+05 2.768687E+04 2.921869E+04
    15      5.261  -4.515637E+04-7.895711E+04 7.266473E+03
    16      5.301  -3.165672E+04-2.039563E+05 6.853066E+03
    17      5.415  -1.580376E+05 7.951596E+04 3.661622E+04
    18      5.461  -2.194453E+04 7.064404E+04 1.161325E+04
    19      5.531  -1.782990E+05 1.418172E+05 3.102347E+04
    20      5.576  -2.799194E+05-2.461280E+04 6.025582E+04
    21      5.669   1.595634E+05 6.051891E+04-2.823643E+04
    22      5.726   2.844460E+03-1.232731E+04-2.315879E+03
    23      5.817   1.191656E+05 2.362657E+05-3.524047E+04
    24      5.878   4.868883E+04-1.087464E+04-1.078890E+04
    25      5.903   1.807121E+05 1.978032E+05-5.120685E+04
    26      5.980   1.610357E+05-6.449381E+04-2.795639E+04
    27      6.023  -9.527540E+04 6.206961E+04 8.434446E+03
    28      6.036  -2.026932E+05 1.256638E+05 3.360857E+04
    29      6.083   7.173998E+04 8.759857E+03-1.343390E+04
    30      6.218  -5.211975E+04 1.437488E+04 8.963594E+03
    31      6.283   1.197094E+04 4.366545E+04-8.608116E+03
    32      6.419   4.693201E+03 1.785113E+04-1.130162E+03
    33      6.447  -1.468977E+03 1.960062E+04 2.007540E+02
    34      6.466   1.028584E+04 1.257356E+04-5.283199E+03
    35      6.574   4.511364E+03-9.883653E+03 2.516036E+01


> 2021年7月11日 18:47,Sharma SRK Chaitanya Yamijala <sharmajncasr at gmail.com> 写道:
> 
> One thing that I could spot is your SCC tolerance value is high. You should at least consider 1e-5 or lower.
> 
> HTH,
> Sharma.
> 
> On Sun, Jul 11, 2021 at 3:45 PM Chencheng Fan <s8chfann at stud.uni-saarland.de <mailto:s8chfann at stud.uni-saarland.de>> wrote:
> Dear DFTB+ developers and users,
> 
> I am using DFTB+ to calculate transition dipole moment between ground state and excited states of the molecules, for example "c1(C=O)cc(N)c(C=O)c(C=O)c1(N)”(benezene derivative in SMILES format). I saw the unreasonable results output by DFTB+.
> 
> Below is my “TDP.DAT" file. As you can see, the magnitude of transition dipole moment is as large as E+06 or E+05 Debye, which is too large for benezene derivatives. Maybe I am wrong, or maybe there are bugs? I also enclosed my two input files for ground state and excited state calculations, as well as “geo_end.gen” file. 
> 
> To compare, I also used Gaussian2016 program to do similar calculations, which gives a reasonable result like several Debye.
> 
> Could you check if there are bugs or find where I am wrong? Thank you very much for your help!
> 
> Best regards
> Chencheng
> 
> ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
> 
> “TDP.DAT”
>      #     w [eV]  Transition dipole (x,y,z) [Debye]
> 
>  =========================================================
> 
>      1      2.031   6.131949E+06-5.912310E+06 1.547522E+05
>      2      2.309   1.425687E+08-3.522297E+08 3.718053E+07
>      3      2.575   6.990917E+06-1.195864E+07 1.560896E+06
>      4      2.706   2.540291E+06-1.885406E+06 4.996668E+05
>      5      3.558   3.789835E+04-3.420982E+05 2.025774E+04
>      6      3.638   2.395250E+06-2.052925E+05 4.662365E+05
>      7      3.784   6.213632E+05 2.655777E+05 8.079874E+04
>      8      4.091   1.789134E+05-4.809087E+04 3.392573E+04
>      9      4.099   7.384366E+04-4.568614E+04 1.314181E+04
>     10      4.105   1.321245E+05-4.088015E+04 2.315489E+04
>     11      4.232  -5.545028E+04 5.576703E+04-1.096753E+04
>     12      4.303   3.121993E+06 1.356360E+05 5.348877E+05
>     13      4.637   3.022992E+03-2.310947E+03-3.608027E+02
>     14      4.769   2.426506E+04-9.721534E+03 4.845503E+03
>     15      5.255  -3.307093E+04 7.958589E+04-7.127908E+03
>     16      5.294  -5.924098E+04 1.717925E+05-1.529312E+04
>     17      5.404  -7.859775E+03-7.372189E+03-2.376946E+02
>     18      5.426   1.089965E+05 9.302225E+04 1.171481E+04
>     19      5.538   2.556451E+05 1.551677E+05 3.731881E+04
>     20      5.586   1.318620E+05-4.210265E+04 2.556480E+04
>     21      5.648  -2.265044E+05 9.355164E+04-4.587144E+04
>     22      5.719   2.304395E+04 2.297392E+04 4.624536E+03
>     23      5.797  -1.071124E+05 2.275764E+05-2.945740E+04
>     24      5.885   1.776589E+05-2.152445E+05 3.915642E+04
>     25      5.948  -5.076180E+04 2.703980E+04-9.630896E+03
>     26      5.970  -2.760882E+04 2.661076E+04-5.311131E+03
>     27      6.029   2.782307E+05 1.396215E+05 4.236757E+04
>     28      6.080   3.011907E+04 1.419100E+04 4.953733E+03
>     29      6.102   4.830399E+04 1.065597E+04 9.198604E+03
>     30      6.154  -5.834737E+04-2.261742E+04-9.942434E+03
>     31      6.297   2.570528E+04-4.906423E+04 1.013159E+04
>     32      6.369   3.005327E+03-3.341125E+03 8.034762E+02
>     33      6.416   7.172637E+03-2.239368E+04 3.053772E+03
>     34      6.513  -2.026772E+03-2.627413E+03-2.600226E+02
>     35      6.639   4.316823E+02 1.760570E+03 2.562028E+00
> ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
> 
> Compared results by Gaussian2016:
> 
>  Ground to excited state transition electric dipole moments (Au):
>        state          X           Y           Z        Dip. S.      Osc.
>          1         0.7598     -1.1999     -0.0047      2.0172      0.1186
>          2        -0.0861      0.0015      0.0199      0.0078      0.0006
>          3         0.0075     -0.0014      0.0057      0.0001      0.0000
>          4        -0.0431      0.0061      0.0010      0.0019      0.0002
>          5        -0.3857      0.1090     -0.0657      0.1650      0.0155
>          6         0.0516      0.0663      0.0213      0.0075      0.0008
>          7         0.2161      0.0483     -0.0319      0.0500      0.0055
>          8         0.0118      0.0148     -0.0119      0.0005      0.0001
>          9        -1.4148     -0.2498      0.0133      2.0643      0.2450
>         10        -0.0183     -0.0098      0.0265      0.0011      0.0001
>         11         0.0435      0.0643      0.0731      0.0114      0.0015
>         12        -0.2358      0.2390     -0.0114      0.1129      0.0160
>         13        -0.6684      0.8691     -0.0259      1.2027      0.1735
>         14        -0.6896     -0.5532      0.0563      0.7847      0.1173
>         15         0.0595     -0.0323      0.0236      0.0051      0.0008
>         16        -0.7143     -0.7069     -0.0125      1.0100      0.1537
>         17        -0.5814      0.2501     -0.0043      0.4006      0.0635
>         18        -0.3658      0.3562     -0.0004      0.2607      0.0417
>         19         1.1539     -0.3796     -0.0088      1.4757      0.2397
>         20         0.7719      0.9020      0.0281      1.4103      0.2335
>         21         0.1342      0.1864      0.0004      0.0528      0.0088
>         22         0.3071      0.2263     -0.0635      0.1496      0.0254
>         23         0.0320     -0.2606      0.0515      0.0716      0.0124
>         24         0.1363      0.1391      0.0081      0.0380      0.0066
>         25         0.1800      0.0779     -0.0303      0.0394      0.0071
>         26        -0.2137      0.0092      0.0235      0.0463      0.0085
>         27        -0.0831     -0.1753      0.0252      0.0383      0.0070
>         28        -0.0400     -0.0017      0.0029      0.0016      0.0003
>         29         0.0305      0.0253      0.0604      0.0052      0.0010
>         30        -0.0145      0.0752     -0.0162      0.0061      0.0012
>         31        -0.1015     -0.0879      0.0201      0.0184      0.0035
>         32         0.0287      0.2253     -0.0195      0.0520      0.0102
>         33        -0.2172     -0.2044      0.0430      0.0908      0.0180
>         34         0.5397      0.2976      0.0427      0.3816      0.0766
>         35        -0.2407     -0.3094     -0.0259      0.1543      0.0311
> ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
> 
> “dftb_in.hsd” for excited state:
> 
> Geometry = GenFormat {
>     <<< "geo_end.gen"
> }
> 
> ExcitedState = Casida{
>    NrOfExcitations = 35
>    Symmetry = singlet
>    WriteMulliken = Yes
>    WriteTotalStateCoeffs = No
>    WriteTransitionDipole = Yes
>    WriteTransitions = Yes
>    }
> Hamiltonian = DFTB{
>    MaxAngularMomentum = {
>       Br = "d"
>       C = "p"
>       Ca = "p"
>       Cl = "d"
>       F = "p"
>       H = "s"
>       I = "d"
>       K = "p"
>       Mg = "p"
>       N = "p"
>       Na = "p"
>       O = "p"
>       P = "d"
>       S = "d"
>       Zn = "d"
>    }
>    MaxSCCIterations = 400
>    SCC = Yes
>    SCCTolerance = 5E-3
>    SlaterKosterFiles = Type2FileNames{
>       Prefix = /nethome/cfan/bin/dftb_skf/
>       Separator = "-"
>       Suffix = ".skf"
>    }
> }
> Options {
>    WriteResultsTag = Yes
> }
> ParserOptions {
>    IgnoreUnprocessedNodes = Yes
> }
> 
> ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
> 
> “dftb_in.hsd” for ground state:
> Geometry = GenFormat {
>     <<< "geo_end.gen"
> }
> 
> Driver = ConjugateGradient{
>    MaxForceComponent = 1E-3
>    MaxSteps = 800
>    }
> Hamiltonian = DFTB{
>    MaxAngularMomentum = {
>       Br = "d"
>       C = "p"
>       Ca = "p"
>       Cl = "d"
>       F = "p"
>       H = "s"
>       I = "d"
>       K = "p"
>       Mg = "p"
>       N = "p"
>       Na = "p"
>       O = "p"
>       P = "d"
>       S = "d"
>       Zn = "d"
>    }
>    MaxSCCIterations = 400
>    SCC = Yes
>    SCCTolerance = 5E-3
>    SlaterKosterFiles = Type2FileNames{
>       Prefix = /nethome/cfan/bin/dftb_skf/
>       Separator = "-"
>       Suffix = ".skf"
>    }
> }
> Options {
>    WriteResultsTag = Yes
> }
> ParserOptions {
>    IgnoreUnprocessedNodes = Yes
> }
> 
> ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
> “geo_end.gen” :
> 
>    22  C
>   C  O  N  H
>     1 1    0.1115675104E+01    0.1111212745E+01   -0.3035902237E+00
>     2 1    0.2251075328E+01    0.2022964250E+01   -0.5876152068E+00
>     3 2    0.3406931415E+01    0.1696900140E+01   -0.7734254423E+00
>     4 1   -0.1453907265E+00    0.1683956027E+01   -0.1375342879E+00
>     5 1   -0.1299819138E+01    0.9170017967E+00    0.1314870108E+00
>     6 3   -0.2509458700E+01    0.1577680799E+01    0.2536118425E+00
>     7 1   -0.1186620758E+01   -0.5006116190E+00    0.2299536734E+00
>     8 1   -0.2375863088E+01   -0.1299894455E+01    0.6257472488E+00
>     9 2   -0.3515256266E+01   -0.8709376263E+00    0.7079034014E+00
>    10 1    0.1008892612E+00   -0.1123222817E+01    0.5094510407E-01
>    11 1    0.2315975160E+00   -0.2601292210E+01    0.5835794937E-01
>    12 2    0.1283655289E+01   -0.3220323386E+01    0.6556984188E-01
>    13 1    0.1256675910E+01   -0.3171362961E+00   -0.2049667538E+00
>    14 3    0.2492396858E+01   -0.8713117298E+00   -0.3550574821E+00
>    15 4    0.1949768634E+01    0.3116003368E+01   -0.6261014282E+00
>    16 4   -0.2404055435E+00    0.2768049412E+01   -0.2083146161E+00
>    17 4   -0.3288581194E+01    0.1061553537E+01    0.6533785233E+00
>    18 4   -0.2473144298E+01    0.2569552409E+01    0.4550099360E+00
>    19 4   -0.2182431033E+01   -0.2377592205E+01    0.9003987810E+00
>    20 4   -0.7361512752E+00   -0.3181152808E+01    0.3286545549E-01
>    21 4    0.2592625631E+01   -0.1883037702E+01   -0.3465640596E+00
>    22 4    0.3271831076E+01   -0.2783616293E+00   -0.6220592671E+00
> 
> 
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> -- 
> Thanks,
> Chaitanya.
> 
> -------------------------
> Sent from my phone. 
> Please excuse me if there are any typos.
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