CCL:G: a question aboutTDDFT calculations with G03



 Sent to CCL by: Yan Zhao [yzhao-x-chem.umn.edu]
 Dear CCLers,
 I have some problems with the TDDFT calculations in Gaussian03.
 
I tried doing TDDFT calculations with G03 to test some functionals developed in our group. Since I am a beginner of using TDDFT, I did a calculation for the CO molecule with PBE0 functional to reproduce the results in Adamo's JCP paper (JCP 111, 2889 (1999)). I can reproduce his results for almost all excited states except the highest Rydberg singlet state corresponding to the state with an experimental excitation energy of 12.4 ev. In Adamo's paper, PBE0 gives 12.01 ev, but I can not extract this excitation energy from my G03 calculations. Moreover I failed to reproduce the HCTH and B3LYP results in Tozer and Handy's paper (JCP 109 10180 (1998)), I also failed to reproduce the B97-2 results in Teale and Tozer's recent paper (JCP 122, 034101 (2005)). They are using CADPAC, not G03. Any suggestions are highly appreciated. The following are my G03 input file and some output information.
 Input
 **************************************************
 #pbe1pbe/6-311++g(d,p) TD=(50-50,Nstates=12) scf=(tight,xqc)
 co pbe0
 0  1
    C             0        0.000000    0.000000   -0.643075
    O             0        0.000000    0.000000    0.482306
 **************************************************
 Output
 **************************************************
 ...............
 Orbital symmetries:
       Occupied  (SG) (SG) (SG) (SG) (PI) (PI) (SG)
       Virtual   (PI) (PI) (SG) (SG) (PI) (PI) (SG) (PI) (PI) (SG)
                 (SG) (PI) (PI) (SG) (SG) (SG) (PI) (PI) (DLTA)
                 (DLTA) (SG) (PI) (PI) (SG) (PI) (PI) (DLTA) (DLTA)
                 (SG) (PI) (PI) (SG) (PI) (PI) (SG) (SG) (SG)
    96 initial guesses have been made.
 ................
 ................
 Excited state symmetry could not be determined.
 Excited State  16:   Triplet-?Sym   11.2347 eV  110.36 nm  f=0.0000
       4 ->  9         0.10254
       7 -> 12         0.44192
       7 -> 13         0.52545
 Excited State  17:   Singlet-SG    11.3361 eV  109.37 nm  f=0.1947
       7 -> 11         0.69676
 Excited state symmetry could not be determined.
 Excited State  18:   Singlet-?Sym   11.4874 eV  107.93 nm  f=0.0508
       7 -> 12         0.24432
       7 -> 13         0.65817
 Excited state symmetry could not be determined.
 Excited State  19:   Singlet-?Sym   11.4874 eV  107.93 nm  f=0.0508
       7 -> 12         0.65817
       7 -> 13        -0.24432
 Excited state symmetry could not be determined.
 Excited State  20:   Triplet-?Sym   11.9391 eV  103.85 nm  f=0.0000
       4 ->  8         0.69457
       4 ->  9        -0.11693
       4 -> 12        -0.10390
       7 -> 12        -0.13267
 Excited state symmetry could not be determined.
 Excited State  21:   Triplet-?Sym   11.9391 eV  103.85 nm  f=0.0000
       4 ->  8         0.11693
       4 ->  9         0.69457
       4 -> 13        -0.10390
       7 -> 13        -0.13267
 Excited state symmetry could not be determined.
 Excited State  22:   Singlet-?Sym   13.1752 eV   94.10 nm  f=0.0665
       5 -> 10         0.69565
       6 -> 10        -0.10395
 Excited state symmetry could not be determined.
 Excited State  23:   Singlet-?Sym   13.1752 eV   94.10 nm  f=0.0665
       5 -> 10         0.10395
       6 -> 10         0.69565
 Excited state symmetry could not be determined.
 Excited State  24:   Singlet-?Sym   13.1819 eV   94.06 nm  f=0.2280
       4 -> 10        -0.13503
       5 ->  9         0.34048
       5 -> 13         0.22450
       6 ->  8         0.34048
       6 -> 12         0.22449
       7 -> 14        -0.23139
 **************************************************
 Yan Zhao
 Department of Chemistry
 University of Minnesota