[molpro-user] Degeneracy in MRCI calculation

[Hyungjun Kim]

Dear Molpro users,


Here is my input. 


SO calculation using ECP follows the example in the manual.


Molecular orbital average is performed according to the Peterson's advice.


---------------------------------------------


memory,1000,m;


gprint,basis;
gprint,orbital;
gthresh,energy=1.d-8;


!symmetry,x,y,z
geometry={Hf}


basis=aug-cc-pVTZ-PP




{rhf,maxit=100
   occ,4,1,1,0,1,0,0,0
closed,2,1,1,0,1,0,0,0
    wf,12,1,2;
OrbPrint,3
}


{multi;
   occ,4,1,1,1,1,1,1,0;
closed,1,1,1,0,1,0,0,0;
config;
    wf,12,1,2;state,1;
    select
    con,2 1 1 0 0 0
   wf,12,4,2;state,2;
    select
    con,2 1 0 1 0 0
    con,2 0 1 1 0 0
    con,2 0 0 0 1 1
   wf,12,6,2;state,2;
    select
    con,2 1 0 0 1 0
    con,2 0 1 0 1 0
    con,2 0 0 1 0 1
   wf,12,7,2;state,2;
    select
    con,2 1 0 0 0 1
    con,2 0 1 0 0 1
    con,2 0 0 1 1 0
}


{ci;
   occ,4,1,1,1,1,1,1,0;
  core,1,1,1,0,1,0,0,0;
     wf,12,1,2;state,1;save,6000.2}
{ci;
   occ,4,1,1,1,1,1,1,0;
  core,1,1,1,0,1,0,0,0;
     wf,12,4,2;state,2;save,6200.2}
{ci;
   occ,4,1,1,1,1,1,1,0;
  core,1,1,1,0,1,0,0,0;
     wf,12,6,2;state,2;save,6300.2}
{ci;
   occ,4,1,1,1,1,1,1,0;
  core,1,1,1,0,1,0,0,0;
     wf,12,7,2;state,2;save,6400.2}


text, mrci
{ci;hlsmat,ecp,6000.2,6200.2,6300.2,6400.2}


Best regards,
-Hyungjun




-----------------------원본메일-----------------------
보낸사람 : "Peterson, Kirk" <kipeters at wsu.edu>
받는사람: Hyungjun Kim <hyungjun96 at kaist.ac.kr>
참 조: molpro-user molpro-user <molpro-user at molpro.net>
보낸날짜: 2014-12-14 01:57:02 GMT +0900 (ROK)
제목: Re: [molpro-user] Degeneracy in MRCI calculation





Dear Hyungjun,


please post an input (to the list, not just to me).


best regards,


-Kirk



On Dec 12, 2014, at 10:55 PM, Hyungjun Kim <hyungjun96 at kaist.ac.kr> wrote:


p{margin:0;padding:0;}


Dear Molpro users,



I have tried to get MRCISD energy and spin orbit coupling (SOC) for 3F (term symbol) Hf atom. (Electronic configuration of Hf atom is 6s2, 5d2)



MRCISD energy with the active space of 5d and 6s is obtained without an accurate degeneracy.

(7 states, (1Ag, 2B1g, 2B2g, 3B2g) should have the same energy.)



I have a similar problem for Y atom (5s2 4d1) case, and the problem can be solved according to the Peterson's advice to increase an active space.



The increased active space for Hf atom including 5s (which is semi core orbital) gives the improved result. The energy difference is reduced to 10^-6 scale but the energy level of 3F are not still perfectly degenerate.



Could you provide me to recover the degeneracy in MRCI calculation?



Any comments are welcome.



Best regards,








---------------------------------------------------
Hyungjun Kim, Ph. D. Student,
Quantum Chemistry Laboratory, Department of Chemistry,
Korea Advanced Institute of Science and Technology [KAIST],
Daejeon 305-701, Korea
e-mail: hyungjun96 at kaist.ac.kr or
hyungjun96 at gmail.com

phone : +82-42-350-2861


mobile phone : +82-10-8537-5051


web : 
http://qclab.kaist.ac.kr









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