[molpro-user] Frequency calculation

Jayashree yfpjaya at gmail.com
Sat Oct 4 23:49:54 BST 2008


Two things -
1. I need to have a UHF input, since I am dealing with a doublet.
2. The present calculation is a conical intersection between A' and A"
states. This is same as the conical intersection at the C3v geometry of
methoxy molecule. In that case, I cannot have 2 states in the symmetry 1.

But in any case, I tried the input given to me by you, and it terminates
with the following message - (this is the section of output of MULTI
program..the UHF and optg calculations run ok.
1PROGRAM * MULTI (Direct Multiconfiguration SCF)       Authors: P.J.
Knowles, H.-J. Werner (1984)     S.T. Elbert (1988)
 Number of closed-shell orbitals:  3 (  3 )
 Number of active  orbitals:       6 (  6 )
 Number of external orbitals:     37 ( 37 )
 State symmetry 1
 Number of electrons:    11    Spin symmetry=Doublet   Space symmetry=1
 Number of states:        2
 Number of CSFs:          6   (6 determinants, 6 intermediate states)
 NOEXTRA OPTION SET FOR FREQUENCY CALCULATION
 Molecular orbitals read from record     2200.2  Type=UHF/NATURAL (state
1.1)
 Wavefunction dump at record             2140.2
 Convergence thresholds  0.10E-05 (gradient)  0.10E-07 (energy)  0.10E-02
(step length)
 Weight factors for state symmetry  1:    0.50000   0.50000
 Number of orbital rotations:     351     (  18 Core/Active  111
Core/Virtual   0 Active/Active  222 Active/Virtual)
 Total number of variables:       363
 ITER. MIC  NCI  NEG     ENERGY(VAR)     ENERGY(PROJ)   ENERGY CHANGE
GRAD(0)  GRAD(ORB)   GRAD(CI)     STEP       TIME
 ?WARNING, SMALL DIAGONAL HESSIAN ELEMENT FOR ROTATION 3.1 -  4.1
D1E=-0.248D-06  D2E= 0.421D-07
 ?WARNING, SMALL DIAGONAL HESSIAN ELEMENT FOR ROTATION 3.1 -  5.1
D1E=-0.632D-07  D2E= 0.135D-07
   1   60    7    0    -114.40430384    -114.40955138   -0.00524754
0.05457236 0.00064851 0.00000000  0.44D-01      0.35
 ERROR EXIT
 CURRENT STACK:      MAIN
   2  201   15    0    -114.40957522    -114.40957745   -0.00000223
0.00273117 0.00003244 0.00000000  0.10D-02      1.03
   3   60   16    0    -114.40957745    -114.40957745    0.00000000
0.00003241 0.00000000 0.00000000  0.28D-04      1.56
 ** WVFN ****  CONVERGENCE REACHED, FINAL GRADIENT:  0.42D-09
 CPMCSCF calculation required for state-averaged gradient calculation.
Please add
 CPMCSCF,GRAD,STATE=istate.isym
 to the mcscf/casscf input, where istate.isym specifies the state for which
the gradients are required.
 Note that gradients for state-averaged MCSCF can only be computed with
segmented basis sets.
 For more details, please refer to the MOLPRO manual.
 ? Error
 ? Missing cpmcscf
 ? The problem occurs in musave
-----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
If I use the following input indicating that the intersection is of states
of different symmetry, it terminates with the following message -
 NOEXTRA OPTION SET FOR FREQUENCY CALCULATION

 ?STATE SYMMETRY NOT POSSIBLE: 2

My input looks like this -
basis=6-311++G
geomtype={zmat}
geometry={Angstrom;nosym
          c;
          o,c,oc;
          h1,c,h1c,o,h1co;
          h2,c,h1c,o,h1co,h1,120.0;
          h3,c,h1c,o,h1co,h1,240.0}
oc=1.410000, h1c=1.100000, h1co=109.100000

 {uhf} !uhf input without symmetry
 put,molden,met_uhf_6311++g.molden

 {optg,space=zmat}
 put,molden,met_opt_6311++g.molden

 {casscf;
  occ,9;
  closed,3;
  wf,17,1,1;
  state,1;
  weight,0.5
  wf,17,2,1;
  state,1;
  weight,0.5
  start,orbital=2200.2

  CPMCSCF,HESS}
 {optg,startcmd=casscf}
 put,molden,met_cas_6311++g_con.molden
 {frequencies}

Any hope of calculating frequencies keeping symmetry in the input?
Thanks
Jayashree

On Sat, Oct 4, 2008 at 11:21 AM, Kirk Peterson <kipeters at wsu.edu> wrote:

> The analytical MCSCF hessian calculation can only be performed without
> symmetry.  I'm not sure about state-averaged wavefunctions, but you can try
> put a "nosym" in your geometry block after "Angstrom", comment out your rhf
> input, and then in your casscf input change this to something like:
>  {casscf;
>   occ,9;
>   closed,3;
>   wf,17,1,1;
>   state,2;
>   CPMCSCF,HESS}
>
>
> -Kirk
>
> On Oct 3, 2008, at 1:18 PM, Jayashree wrote:
>
> I have located a conical intersection corresponding to the C3v geometry in
> methoxy molecule. I would like to calculate the normal mode frequencies of
> the molecule at this geometry. If I try to give the command 'frequencies'
> below 'optg', I get the following error:
>  ?STATE SYMMETRY NOT POSSIBLE: 2
> How do I calculate the frequencies?
>
> This is how my input file looks like -
> ***,methoxy
> memory,128,m
> file,2,met_cas_6311++g.wf,new;
> punch,met_cas_6311++g.pun
>
> gprint,basis,orbitals=6,civector
>
> basis=6-311++G
> geomtype={zmat}
> geometry={Angstrom;
>           c;
>           o,c,oc;
>           h1,c,h1c,o,h1co;
>           h2,c,h1c,o,h1co,h1,120.0;
>           h3,c,h1c,o,h1co,h1,240.0}
> oc=1.410000, h1c=1.100000, h1co=109.100000
>
>  {uhf !uhf input with symmetry
>   occ,7,2
>   open,7.1
>   wf,17,1,1}
>  put,molden,met_uhf_6311++g.molden
>
>  {optg,space=zmat}
>  put,molden,met_opt_6311++g.molden
>
>  {casscf;
>   occ,7,2;
>   closed,3,0;
>   wf,17,1,1;
>   state,1;
>   weight,0.5
>   wf,17,2,1;
>   state,1;
>   weight,0.5
>   start,orbital=2200.2
> !put,molden,met_cas_6311++g_gs.molden
>
>   CPMCSCF,GRAD,1.1,spin=0.5,accu=1.0d-7,record=5101.1
>   CPMCSCF,GRAD,1.2,spin=0.5,accu=1.0d-7,record=5102.1}
>   put,molden,met_cas_6311++g.molden
>
>   {Force
>   SAMC,5101.1
>   CONICAL,6100.1}
>
>   {Force
>   SAMC,5102.1
>   CONICAL,6100.1}
>
>  {optg,startcmd=casscf}
>  put,molden,met_cas_6311++g_con.molden
>  {frequencies}
>
>
> --
> Jayashree
>  _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user
>
>
>


-- 
Jayashree
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