Ceilidh ... Re: Hessian at MCSSCF level of theory.

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Re: Hessian at MCSSCF level of theory.

Hi Pasha,

Is the equilibrium geometry symmetric? Looks like CASSCF solution
at equilibrium geometry is not stable with respect to small
geometric distortions that lower the symmetry.

Kind regards,
Alex

On Sun Jun 5 '11 7:13am, Solntsev Pasha wrote
---------------------------------------------
>Hi all.

>I am modeling reaction and i successfully did geometry optimization of one product. Then i started hessian job (directly after optimize and separately). But i don't know is it ok if initial mcscf wave function was converged but if we start hessian i can't converge it. Also, just to be sure, if we increase active space we also change energy. So we have to use same active space for all products. Am i right?

>!My input file for hessian job:
> $SYSTEM MWORDS=50 kdiag=0 fastf=.t. nojac=100 $END
> $CONTRL RUNTYP=hessian wide=.t. inttyp=hondo
> icut=11 itol=30 d5=.t. coord=cart exetyp=run $end
>! exra speed
> $contrl fstint=.t. gencon=.t. $END
> $trans mptran=2 cuttrf=1d-13 dirtrf=.t. aoints=dup altpar=.t. mode=112 $end
> $smp call64=.t. $end
> $p2p p2p=.t. dlb=.t. xdlb=.t. $end
>! CASSCF(10,7) setup
> $drt group=c2 fors=.t. foci=.f. nmcc=17 ndoc=5 nval=2 $end
> $mcscf cistep=guga soscf=.t. fors=.t. acurcy=1d-7 engtol=1d-12 maxit=100 $end
> $GUGEM pack2=.t. dirci=.t. $end
> $gugdia nstate=3 $end
> $gugdm iroot=1 $end
> $gugdm2 wstate(1)=1,-0 $end
>! end CASSCF
> $STATPT OptTol=1e-6 NStep=500 $END
> $CONTRL SCFTYP=mcscf $END
> $CONTRL ICHARG=0 MULT=1 $END
> $BASIS GBASIS=N311 NGAUSS=6 $END
> $BASIS NDFUNC=1 NPFUNC=1 $END
> $BASIS DIFFSP=.TRUE. $END
> $force vibanl=.t. $end
> $guess guess=moread norb=180 $end
> $moorth nostf=1 nozero=1 syms=1 symden=1 symvec=1 $end
> $SCF DIRSCF=.TRUE. FDIFF=.f. nconv=6 $END
> $DATA
>1,2-dihydrobenzene C2 CASSCF(4,4) opt 6-311+G(d,p) 2 states
>CN 2

>coord's
>$end
>$vec
>...
>$end

>!Successfully converged mcscf wave function from hessian output file.

> ITER TOTAL ENERGY DEL(E) LAG.ASYMM. SQCDF MICIT DAMP

> 1 -231.910350443 -231.910350443 0.004028 5.456E-04 3 0.0000

> ----------START APPROXIMATE SECOND ORDER MCSCF----------

> 2 -231.910397148 -0.000046704 0.000853 3.195E-05 1 0.0000

> 3 -231.910410784 -0.000013636 0.000346 2.027E-05 1 0.0000

> 4 -231.910413025 -0.000002242 0.000111 6.494E-06 1 0.0000

> 5 -231.910413174 -0.000000148 0.000048 1.783E-05 1 0.0000

> 6 -231.910413266 -0.000000092 0.000020 1.592E-05 1 0.0000

> 7 -231.910413315 -0.000000049 0.000042 7.625E-05 1 0.0000

> 8 -231.910413391 -0.000000075 0.000054 4.082E-05 1 0.0000

> 9 -231.910413432 -0.000000041 0.000035 1.208E-05 1 0.0000

> 10 -231.910413450 -0.000000019 0.000010 6.767E-07 1 0.0000

> 11 -231.910413455 -0.000000005 0.000004 3.958E-07 1 0.0000

> 12 -231.910413457 -0.000000002 0.000006 6.486E-07 1 0.0000

> 13 -231.910413459 -0.000000002 0.000004 1.164E-06 1 0.0000

> 14 -231.910413460 -0.000000001 0.000004 1.066E-06 1 0.0000

> 15 -231.910413461 -0.000000001 0.000003 3.720E-07 1 0.0000

> 16 -231.910413462 -0.000000001 0.000003 4.007E-08 1 0.0000

> 17 -231.910413462 0.000000000 0.000001 8.824E-09 1 0.0000

> 18 -231.910413462 0.000000000 0.000001 7.101E-09 1 0.0000

> 19 -231.910413462 0.000000000 0.000001 1.065E-08 1 0.0000

> 20 -231.910413462 0.000000000 0.000001 1.469E-08 1 0.0000

> 21 -231.910413462 0.000000000 0.000000 8.684E-09 1 0.0000

> 22 -231.910413462 0.000000000 0.000000 1.355E-09 1 0.0000

> 23 -231.910413462 0.000000000 0.000000 2.482E-10 1 0.0000

> 24 -231.910413462 0.000000000 0.000000 4.682E-10 1 0.0000
>
>
>.....

>1 ATOM 2

> -------------------

> COORD 1 NUCLEAR COORDINATES

> -------------------

> VIB 1
>
>
>......
> ITER TOTAL ENERGY DEL(E) LAG.ASYMM. SQCDF MICIT DAMP

> 1 -231.910393044 -231.910393044 0.001028 2.662E-04 1 0.0000

> ----------START APPROXIMATE SECOND ORDER MCSCF----------

> 2 -231.910399828 -0.000006784 0.001005 5.698E-05 1 0.0000

> 3 -231.910412914 -0.000013086 0.000208 2.861E-02 1 0.0000

> 4 -231.911152998 -0.000740085 0.015799 2.468E-02 1 0.0000

> 5 -231.910264540 0.000888458 0.009864 6.513E-04 1 0.0000

> 6 -231.910406841 -0.000142301 0.000693 2.248E-04 1 0.0000

> 7 -231.910415707 -0.000008865 0.000382 4.649E-03 1 0.0000

> 8 -231.910491655 -0.000075948 0.001642 4.230E-03 1 0.0000

> 9 -231.910403098 0.000088556 0.000862 2.063E-03 1 0.0000

> 10 -231.910408186 -0.000005088 0.000881 2.834E-03 1 0.0000

> 11 -231.910418249 -0.000010063 0.001596 2.828E-03 1 0.0000

> 12 -231.910402900 0.000015349 0.001042 2.592E-03 1 0.0000

> 13 -231.910412730 -0.000009830 0.001382 5.778E-02 1 0.0000

> SOSCF IS SCALING ROTATION ANGLE MATRIX, DXMAX= 0.531671

> 14 -231.910204792 0.000207938 0.009660 2.208E-01 1 0.0000

> SOSCF IS SCALING ROTATION ANGLE MATRIX, DXMAX= 0.241842

> 15 -231.910033535 0.000171257 0.014551 2.515E-01 1 0.0000

> SOSCF IS SCALING ROTATION ANGLE MATRIX, DXMAX= 0.216357

> 16 -231.906707811 0.003325724 0.038135 2.061E-01 1 0.0000

> 17 -231.909646890 -0.002939080 0.019429 6.125E-02 1 0.0000

> 18 -231.910243241 -0.000596350 0.016248 3.060E-02 1 0.0000

> 19 -231.909851285 0.000391956 0.023419 1.785E-02 1 0.0000

> 20 -231.910065584 -0.000214299 0.019220 2.722E-03 1 0.0000

> 21 -231.909929950 0.000135634 0.019800 1.285E-02 1 0.0000

> 22 -231.910276407 -0.000346457 0.017552 6.407E-03 1 0.0000

> 23 -231.910559158 -0.000282751 0.016592 1.548E-01 1 0.0000

> 24 -231.909807670 0.000751488 0.009383 6.541E-02 1 0.0000

> 25 -231.911820110 -0.002012439 0.009442 1.982E-01 1 0.0000

> 26 -231.911160884 0.000659226 0.015096 1.086E-01 1 0.0000

> 27 -231.912233780 -0.001072896 0.014496 1.587E-01 1 0.0000

> 28 -231.912091155 0.000142624 0.009406 6.585E-02 1 0.0000
>
>
>As you can see we have problem with wave function. May be i missed something in input file? I will be very appreciate for any help, advices, notes, recommendations related to reaction study at mcscf level of theory.

>Best wishes,

>Pavel.
>
>
>
>
>

Sun Jun 5 '11 1:19pm

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