[molpro-user] Size consistency issue

[Kirk Peterson]

Dear George,

I would look carefully at the orbitals you obtain from multi at long range.  In particular it could happen that the the 1s, 2s, and /or 2p orbitals might not be arranged in canonical order so that you’re not correlating what you want. This can happen when an occupation is very nearly 2.0 but not quite. You might have to add an additional closed directive at long range.

regards,

-Kirk

> On Feb 10, 2016, at 10:36 AM, george <george.iitm at gmail.com> wrote:
> 
> Dear molpro users
> 
> 
>        I am computing potential energy curve for ground state O2+ at multi level using av5z basis set. This dissociates to O(3P)+O+(4S) fragments. Now I add the energies of these two fragments and get -149.18369960 hartrees at the same level. When I look at the energies of curve at 100 angstrom, the multi value at this long distance is  -149.13557933 hartrees. I wonder why and how this numerical discrepancies arise? My input file is very simple without any complicated keyworkds. Am I missing something relevent to this type of problem? Any suggestion please.
> 
> 
> My input
> 
>  ***,o2+
>  memory,125,m
>  print,orbitals,civector
>                                                                                  !file,1,o2+_ci_d2h_6_1_mar5.int <https://urldefense.proofpoint.com/v2/url?u=http-3A__ci-5Fd2h-5F6-5F1-5Fmar5.int&d=CwMGaQ&c=C3yme8gMkxg_ihJNXS06ZyWk4EJm8LdrrvxQb-Je7sw&r=mqaXWsZ0ghQR-pXvPLjY_g&m=Y-rinrtgpeuElJz63uC2MyFZ28u4TampljWeOskYCtU&s=Al9dQX1e7U1uXfGObu48-lciI70ME3iBCTGCDeB9VMY&e=>
>                                                                                  !file,2,o2+_ci_d2h_6_1_mar5.wfu
>                         !symmetry,nosym                                                                                 !symmetry,x
>                                                          !rcm=[1.11780256,0.7,0.75,0.8,0.85,0.9,0.95,1,1.025,1.05,1.075,1.1,1.110,\
>                                                                             !      1.125,1.15,1.175,1.2,1.25,1.3,1.35,1.4,1.5,1.6,\
>  !      1.7,1.8,1.9,2,2.125,2.25,2.5,2.75,3,3.25,3.375,3.5,3.625,3.75,4,4.25,4.5,4.75,5,5.25,5.5,5.75,6,6.5,7,7.5,8,9,10,11,12,13,14,15,16,18,20,21,22,23,24,25] ANG
>  rcm=[100] ANG
> 
>  geometry                                                                        !geometry specification, using z-matrix
>  o1
>  o2,o1,r
>  end
> 
>  basis=aug-cc-pV5Z
> 
>  do i=1,#rcm
> 
>  r=rcm(i)
> 
>  {multi;maxiter,40;config;pspace,0.1;wf,15,7,1;dm}
>  emulti_gs(i)=energy(1)
>                                                                                  !{ci;option,maxiti=10000;wf,15,6,1}
>                                                                                  !eci_gs(i)=energy(1)
>                                                                                  !eci_david(i)=energd(1)
> 
>  {table,rcm,emulti_gs
>  Title,Results for O2+ dissociation 2Pi_g state
>  format,'(f15.8,f30.15)'}
> 
>                                                                                  !{table,rcm,eci_gs
>                                                                                  !format,'(f15.8,f30.15)'}
> 
>                                                                                  !{table,rcm,eci_david
>                                                                                  !format,'(f15.8,f30.15)'}
> 
>  end do
> 
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