[molpro-user] about dissociation energy of BrCl and CrCu

[Wang Mingwei]

Hello everyone,
When I calculated the dissociation energy of the ground state of a diatomic
molecule BrCl, it is found that the calculated result (De= 2.163eV) is lower
than the experimental one (De=2.221eV). Our result was derived by fitting
the PEC of the ground state using Le Roy's LEVEL program. From the
difference between the minimum energy of the PEC of the ground state and the
total energy of two isolated atoms worse 1.924eV was got.


Similar result was got for the CrCu molecule. Fitting the PEC of the ground
state using Le Roy's LEVEL program we got De=1.03eV , while the experimental
De=1.36eV. Also worse 0.86eV was got from the difference between the minimum
energy of the PEC of the ground state and the total energy of two isolated
atoms.
So is this an intrinsic problem of the theoretical method or a problem
related to the calculated method that I selected?
Thank you very much.
Best regards,
mingwei

The following is our input file:
Brcl:
***BrCl***
 memory,90,m
 gprint,orbital,basis
 geometry={angstrom;
           BR;
           CL,BR,2.587;
           }
 basis={spdf,BR,cc-pVTZ-DK;c;
        s,BR,0.455930000E-01;
        p,BR,0.351420000E-01;
        d,BR,0.104700000E+00;
        f,BR,0.258000000E+00;

        spdf,CL,cc-pVTZ-DK;c;
        s,CL,0.591000000E-01;
        p,CL,0.419000000E-01;
        d,CL,0.135000000E+0;
        f,CL,0.312000000E+00;
 }

 dkroll=1;

 hf;
 occ,13,6,6,1;wf,52,1,0;

 multi;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;
 wf,52,1,0;state,3;wf,52,1,2;state,3;wf,52,2,0;state,2;wf,52,2,2;state,2;
 wf,52,3,0;state,2;wf,52,3,2;state,2;wf,52,4,0;state,2;wf,52,4,2;state,3;

 mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,1,0;
 restrict,0,1,15.1;option,nstati=6;state,3;
 mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,1,2;
 restrict,0,1,15.1;option,nstati=6;state,3;

 mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,2,0;
 restrict,0,1,15.1;option,nstati=4;state,2;

 mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,2,2;
 restrict,0,1,15.1;option,nstati=4;state,2;

 mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,4,0;
 restrict,0,1,15.1;option,nstati=4;state,2;

 mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,4,2;
 restrict,0,1,15.1;option,nstati=6;state,3;
--------------------------------

***BrCl***
memory,90,m
gprint,orbital,basis
geometry={angstrom;
           BR;
           CL,BR,2.587;
           }
e_cisd(1) =-3065.65765713
e_cisd(2) =-3065.55955517
e_cisd(3) =-3065.55577986
e_cisd(4) =-3065.60342217
e_cisd(5) =-3065.57629849
e_cisd(6) =-3065.60342217
e_cisd(7) =-3065.57629849
e_cisd(8) =-3065.55955517
e_cisd(9) =-3065.55231646
e_cisd(10)=-3065.56835310
e_cisd(11)=-3065.55071012
e_cisd(12)=-3065.54922167
e_cisd(13)=-3065.61818535
e_cisd(14)=-3065.58110275
e_cisd(15)=-3065.61818535
e_cisd(16)=-3065.58110275
e_cisd(17)=-3065.56509009
e_cisd(18)=-3065.55071012
e_cisd(19)=-3065.44262005

basis={spdf,BR,cc-pVTZ;
       spdf,CL,cc-pVTZ;
 }

hf;
occ,13,6,6,1;wf,52,1,0;

multi;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;
wf,52,1,0;state,3;wf,52,1,2;state,3;wf,52,2,0;state,2;wf,52,2,2;state,2;
wf,52,3,0;state,2;wf,52,3,2;state,2;wf,52,4,0;state,2;wf,52,4,2;state,3;

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,1,0;
option,nstati=6;state,3;save,4010.1
noexc

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,2,0;
option,nstati=4;state,2;save,4020.1
noexc

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,3,0;
option,nstati=4;state,2;save,4030.1
noexc

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,4,0;
option,nstati=4;state,2;save,4040.1
noexc

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,1,2;
option,nstati=6;state,3;save,4012.1
noexc

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,2,2;
option,nstati=4;state,2;save,4022.1
noexc

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,3,2;
option,nstati=4;state,2;save,4032.1
noexc

mrci;occ,15,6,6,1;core,8,3,3;closed,10,4,4,1;wf,52,4,2;
option,nstati=6;state,3;save,4042.1
noexc

lsint

hlsdiag=e_cisd;

mrci;hlsmat,ls,4010.1,4020.1,4030.1,4040.1,4012.1,4022.1,4032.1,4042.1;
print,HLS=2,VLS=0;

CrCu:

***CrCu
memory,250,m
gprint,orbital,basis
geometry={angstrom
Cr
Cu,Cr,2.468}

basis={spdf,Cr,Bauschlicher-ANO;c,
spdf,Cu,Bauschlicher-ANO;c}

dkroll=1
uhf
occ,16,6,6,2
closed,12,5,5,1
wf,53,1,7
maxiter,100
orbprint,10

multi
occ,16,6,6,2
core,10,4,4
wf,53,4,3;state,3

multi
occ,16,6,6,2
core,10,4,4;closed,10,5,5
wf,53,4,3;state,3

multi
occ,16,6,6,2
core,10,4,4;closed,10,4,4
wf,53,4,3;state,3

mrci
occ,16,6,6,2
core,10,4,4;closed,10,4,4
wf,53,1,5;
pspace,0.2
natorb,print
ed15=energd
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