Author Topic: Different excited state energy between a2u 200 and a2u 300 TDDFT calculation.  (Read 4155 times)

kmlin

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Dear all,
My structure of TDDFT calculation is a linear chain of Na 40. The structure was optimized by VASP. Therefore, VASP structure output file CONTCAR was converted to coor and the structure relaxation was not performed by Turbomole. The dscf calculation is converged, since there is a energy file in my calculation directory. The escf calculation for a2u 200 and a2u 300 are calculated separately. The difference of control file between them is only the excited state number of a2u. However, they have different excited state energy after the 41th singlet excitation.

For a2u 200 calculation
40 singlet a2u excitation
Excitation energy / eV:                 0.9921363352821709
41 singlet a2u excitation
Excitation energy / eV:                  1.003326534071252

For a2u 300 calculation
40 singlet a2u excitation
Excitation energy / eV:                 0.9921363510817086
41 singlet a2u excitation
Excitation energy / eV:                  4.922113748874488

Both of above dscf calculation are calculated separately.
The control file for a2u 200 calculation is as follows,
Code: [Select]
$title
$operating system unix
$symmetry d6h
$redundant    file=coord
$coord    file=coord
$user-defined bonds    file=coord
$atoms
na 1-40                                                                        \
   basis =na def2-TZVPP
$basis    file=basis
$rundimensions
   dim(fock,dens)=982980
   natoms=40
   nshell=480
   nbf(CAO)=1400
   nbf(AO)=1280
   dim(trafo[SAO<-->AO/CAO])=3280
   rhfshells=1
$scfmo   file=mos
$closed shells
 a1g     1-70                                   ( 2 )
 e1g     1-20                                   ( 2 )
 a2u     1-70                                   ( 2 )
 e1u     1-20                                   ( 2 )
$scfiterlimit      100
$thize     0.10000000E-04
$thime        5
$scfdump
$scfintunit
 unit=30       size=0        file=twoint
$scfdiis
$scforbitalshift  automatic=.1
$drvopt
   cartesian  on
   basis      off
   global     off
   hessian    on
   dipole     on
   nuclear polarizability
$interconversion  off
   qconv=1.d-7
   maxiter=25
$optimize
   internal   on
   redundant  on
   cartesian  off
   global     off
   basis      off   logarithm
$coordinateupdate
   dqmax=0.3
   interpolate  on
   statistics    5
$forceupdate
   ahlrichs numgeo=0  mingeo=3 maxgeo=4 modus=<g|dq> dynamic fail=0.3
   threig=0.005  reseig=0.005  thrbig=3.0  scale=1.00  damping=0.0
$forceinit on
   diag=default
$energy    file=energy
$grad    file=gradient
$forceapprox    file=forceapprox
$lock off
$dft
   functional pbe
   gridsize   m5
$scfconv   6
$scfdamp   start=0.700  step=0.050  min=0.050
$scfinstab rpas
$soes
 a2u        200
$rpacor  14000
$denconv 1d-7
$last step     escf
$statistics  off
$2e-ints_shell_statistics    file=metastase
$orbital_max_rnorm 0.39111228241719E-04
$last SCF energy change = -6487.1377
$dipole from dscf
  x     0.00000000000000    y     0.00000000000000    z    -0.00000000001175    a.u.
   | dipole | =    0.0000000000  debye
$end

The control file for a2u 300 calculation is as follows,
Code: [Select]
$title
$operating system unix
$symmetry d6h
$redundant    file=coord
$coord    file=coord
$user-defined bonds    file=coord
$atoms
na 1-40                                                                        \
   basis =na def2-TZVPP
$basis    file=basis
$rundimensions
   dim(fock,dens)=982980
   natoms=40
   nshell=480
   nbf(CAO)=1400
   nbf(AO)=1280
   dim(trafo[SAO<-->AO/CAO])=3280
   rhfshells=1
$scfmo   file=mos
$closed shells
 a1g     1-70                                   ( 2 )
 e1g     1-20                                   ( 2 )
 a2u     1-70                                   ( 2 )
 e1u     1-20                                   ( 2 )
$scfiterlimit      100
$thize     0.10000000E-04
$thime        5
$scfdump
$scfintunit
 unit=30       size=0        file=twoint
$scfdiis
$scforbitalshift  automatic=.1
$drvopt
   cartesian  on
   basis      off
   global     off
   hessian    on
   dipole     on
   nuclear polarizability
$interconversion  off
   qconv=1.d-7
   maxiter=25
$optimize
   internal   on
   redundant  on
   cartesian  off
   global     off
   basis      off   logarithm
$coordinateupdate
   dqmax=0.3
   interpolate  on
   statistics    5
$forceupdate
   ahlrichs numgeo=0  mingeo=3 maxgeo=4 modus=<g|dq> dynamic fail=0.3
   threig=0.005  reseig=0.005  thrbig=3.0  scale=1.00  damping=0.0
$forceinit on
   diag=default
$energy    file=energy
$grad    file=gradient
$forceapprox    file=forceapprox
$lock off
$dft
   functional pbe
   gridsize   m5
$scfconv   6
$scfdamp   start=0.700  step=0.050  min=0.050
$scfinstab rpas
$soes
 a2u        300
$rpacor  14000
$denconv 1d-7
$last step     escf
$statistics  off
$2e-ints_shell_statistics    file=metastase
$orbital_max_rnorm 0.39111171692423E-04
$last SCF energy change = -6487.1377
$dipole from dscf
  x     0.00000000000000    y     0.00000000000000    z    -0.00000000001998    a.u.
   | dipole | =    0.0000000001  debye
$end

I do not know why the calculation results are not consistent.

Thanks,

christof.haettig

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You should report this problem to your TURBOMOLE reseller.
Christof