[molpro-user] RSPT2 for an open-shell degenerate state

[Victor G. Solomonik]

Dear Molpro Community,

below please find an input and the main results of the RSPT2 job for
the Ni^3+ ion 4F (ground) and 4P (first excited) states (d^7).

At the RSPT2 level of theory the components of 4F state are not
degenerate if the D_2h symmetry is imposed. Though all three
components of 4P state are always degenerate, an RSPT2 energy of this
state depends on whether the symmetry off or symmetry on option is
used. 

What is wrong in the input? How to achieve a meaningful result for
this particular case using the symmetry?

I would highly appreciate receiving your comments and advice.

Victor

************************************************************
PROGRAM SYSTEM MOLPRO, Version 2009.1, Patch level 20
  ***,Ni^3+ states 4F and 4P
  memory,200,M
  gprint,orbitals=10
  dkroll=1
  geometry={NI}
  basis={spdfg,NI,WCVTZ-DK;c}
  {rhf,MAXIT=250;WF,30,1,0}
 !RHF STATE 1.1 Energy              -1518.625588452147
  {multi
  config;
  wf,25,1,3;
 !MCSCF STATE 1.1 Energy            -1517.017231378072   F
  wf,25,4,3;state,3;
 !MCSCF STATE 1.4 Energy            -1517.017231378048   F
 !MCSCF STATE 2.4 Energy            -1517.017231378041   F
 !MCSCF STATE 3.4 Energy            -1516.919460988586     P
  wf,25,6,3;state,3;
 !MCSCF STATE 1.6 Energy            -1517.017231378058   F
 !MCSCF STATE 2.6 Energy            -1517.017231378020   F
 !MCSCF STATE 3.6 Energy            -1516.919460988666     P
  wf,25,7,3;state,3;
 !MCSCF STATE 1.7 Energy            -1517.017231378057   F
 !MCSCF STATE 2.7 Energy            -1517.017231378018   F
 !MCSCF STATE 3.7 Energy            -1516.919460988662     P
  canonical,ci;
  }
  {rs2,
  core,2,1,1,0,1,0,0,0
  wf,25,1,3
  state,1
  }
 !RSPT2 STATE 1.1 Energy            -1517.659070068412   F
  {rs2,
  core,2,1,1,0,1,0,0,0
  wf,25,4,3
  state,3
  }
 !RSPT2 STATE 1.4 Energy            -1517.667860700780   F  
 !RSPT2 STATE 2.4 Energy            -1517.665874826462   F
 !RSPT2 STATE 3.4 Energy            -1517.586409662105     P  
  {rs2,
  core,2,1,1,0,1,0,0,0
  wf,25,6,3
  state,3
  }
 !RSPT2 STATE 1.6 Energy            -1517.666833251472   F
 !RSPT2 STATE 2.6 Energy            -1517.666924251649   F
 !RSPT2 STATE 3.6 Energy            -1517.586409623237     P  
  {rs2,
  core,2,1,1,0,1,0,0,0
  wf,25,7,3
  state,3
  }
 !RSPT2 STATE 1.7 Energy            -1517.667126446211   F
 !RSPT2 STATE 2.7 Energy            -1517.666629728095   F
 !RSPT2 STATE 3.7 Energy            -1517.586409623231     P
  
  set,zsymel=nosym
  geometry={NI}
  basis={spdfg,NI,WCVTZ-DK;c}
  {rhf,MAXIT=250;
  WF,30,1,0}
 !RHF STATE 1.1 Energy              -1518.625588450472  
  {multi
  config;
  wf,25,1,3;state,10;
  canonical,ci;
  }
 !MCSCF STATE 1.1 Energy            -1517.017231377768  F
 !MCSCF STATE 2.1 Energy            -1517.017231377763  F
 !MCSCF STATE 3.1 Energy            -1517.017231377760  F
 !MCSCF STATE 4.1 Energy            -1517.017231377735  F
 !MCSCF STATE 5.1 Energy            -1517.017231377734  F
 !MCSCF STATE 6.1 Energy            -1517.017231377711  F
 !MCSCF STATE 7.1 Energy            -1517.017231377708  F
 !MCSCF STATE 8.1 Energy            -1516.919460988370    P
 !MCSCF STATE 9.1 Energy            -1516.919460988367    P
 !MCSCF STATE10.1 Energy            -1516.919460988308    P
  {rs2,
  core,5
  wf,25,1,3
  state,10
  }
 !RSPT2 STATE 1.1 Energy            -1517.667328341767  F
 !RSPT2 STATE 2.1 Energy            -1517.667328341855  F
 !RSPT2 STATE 3.1 Energy            -1517.667328341852  F
 !RSPT2 STATE 4.1 Energy            -1517.667328341947  F
 !RSPT2 STATE 5.1 Energy            -1517.667328341568  F
 !RSPT2 STATE 6.1 Energy            -1517.667328341819  F
 !RSPT2 STATE 7.1 Energy            -1517.667328341806  F
 !RSPT2 STATE 8.1 Energy            -1517.587323704799    P
 !RSPT2 STATE 9.1 Energy            -1517.587323704793    P
 !RSPT2 STATE10.1 Energy            -1517.587323704517    P
*************************************************************