[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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