[molpro-user] Frequency calculation
Jayashree
yfpjaya at gmail.com
Sun Oct 5 01:04:04 BST 2008
I am now using my input with symmetry. and with the last line as you
suggested - {frequency,central} and I get the following message -
PROGRAM * HESSIAN
Computing numerical hessian using default procedure for command CASSCF
Symmetry elements for unique displacements: Y
Using no symmetry in wavefunction calculations
Running default procedure: CASSCF000
Numerically approximating hessian using central gradient differences
Task list generated. Total number of displacements: 21
?STATE SYMMETRY NOT POSSIBLE: 2
I have attached my input and output file.
On Sat, Oct 4, 2008 at 6:41 PM, Kirk Peterson <kipeters at wsu.edu> wrote:
>
> If you turn off symmetry, then both the A' and A" have symmetry A and you
> do have two states of the same symmetry. From the look of this output
> though it appears that state-averaged gradients only work with segmented
> basis sets which is not the newer program that can do analytical hessians.
> Your frequency calculation would then calculate the hessian by numerical
> differentiation of the analytical gradient (so disregard my cpmcscf,hess
> input).
> So I would recommend going back to your original input (in symmetry),
> removing the 2nd cpmcscf card, and in the frequency command use:
> freq,central
>
> -Kirk
>
>
> On Oct 4, 2008, at 3:49 PM, Jayashree wrote:
>
> 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
>
>
>
--
Jayashree
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