[molpro-user] About Size consistent problem in O2H+

[CheikhTidiane BOP]

Hi, dear geroge,


To force the potential to decay to zero, it must be uniformly shifted by the corresponding asymptotic value (R = 50 Ang).


Best regards,

Bop

________________________________
De : Molpro-user <molpro-user-bounces at molpro.net> de la part de george <george.iitm at gmail.com>
Envoyé : jeudi 15 décembre 2016 16:44:34
À : molpro-user molpro-user
Objet : [molpro-user] About Size consistent problem in O2H+

Dear users


I am calculating CBS PES of O2H+ ion. When I calculate a single point calculation of X-state keeping the distance between OH+ fragment and O-atom at 50 Ang at CAS/cc-pVQZ level, I get the following energy at CAS level E_cas = -149.8371634 hartrees.

Now, I do the individual calculation at the same level of the OH+ ion and O-atom seperately and I get E_cas(OH+) = -75.02897195 hartrees and E_cas(O) = -74.80987715 hartrees. When I sum, I get E_cas(OH+ and O) = -149.83884910 hartrees. I find that the summed energy and energy of the O2H+ ion calculated at 50 Ang differ by 0.0016857 hartrees which is sizable according to my opinion.

My question is that if there is any way out to reduce this difference to almost zero hartrees (i.e to say about 0.000001 hartrees)

I write below input file I used for each of the above mentioned calculation for the users to find out the possible mistakes in them if any

I will be happy to receive any comments from the experienced users to this issue.

Input file for O2H+ ion at 50 Ang
-----------------------------------------------
 ***,o2hp
print,orbitals,civector
                                                                                !file,1,o2hp_ci_cs_2_1_titan.int<http://o2hp_ci_cs_2_1_titan.int>
file,2,b.wfu
                                                                                !symmetry,x

rcm=[1.258030346,0.9,1,1.1,1.15,1.2,1.25,1.3,1.35,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.05,2.1,2.2,2.3,2.4,2.6,2.8,\
              3,3.2,3.4,3.6,3.8,4,4.5,5,6,8,10,15,20,30,50] ANG

roh=1.008682076 ANG
theta=30 DEGREE

basis=cc-pVQZ

do i=1,#rcm

ro=rcm(i)

symmetry,x
geometry={                                                                      !geometry specification, using z-matrix
 3
 O2HP
O          0         0              -(1/17)*roh
H          0         0              (16/17)*roh
O          0     ro*sin(theta)     ro*cos(theta)
}


{multi;config;wf,16,2,2;state,5;dm}
emulti_gs(i)=energy(1)
emulti_1xs(i)=energy(2)
emulti_2xs(i)=energy(3)
emulti_3xs(i)=energy(4)
emulti_4xs(i)=energy(5)
{ci;option,maxiti=5000;wf,16,2,2;state,5}
eci_gs(i)=energy(1)
eci_1xs(i)=energy(2)
eci_2xs(i)=energy(3)
eci_3xs(i)=energy(4)
eci_4xs(i)=energy(5)

table,rcm,emulti_gs,emulti_1xs,emulti_2xs,emulti_3xs,emulti_4xs
Title,Results for O2H+
table,rcm,eci_gs,eci_1xs,eci_2xs,eci_3xs,eci_4xs

end do

{pop;individual;density,2140.2,charge,state=1.2}
{pop;individual;density,2140.2,charge,state=2.2}
{pop;individual;density,2140.2,charge,state=3.2}
{pop;individual;density,2140.2,charge,state=4.2}
{pop;individual;density,2140.2,charge,state=5.2}

 Input file for OH+ fragment
-------------------------------------------
***,o2h+
print,orbitals,civector
file,1,oh+_ci_c2v_4_1_mar5.int
file,2,oh+_ci_c2v_4_1_mar5.wfu

!rcm=[1.0275782448,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9,0.925,0.95,0.975,1,1.025,1.05,1.075,1.1,1.15,1.2,1.4,1.6,\
!     1.8,2,2.5,3,3.5,4,4.5,5,6,8,10,12,14,16,18,20] ANG
rcm=[1.008682076] ANG

geometry={                                                                      !geometry specification, using z-matrix
o
h o roh
}

basis=cc-pVQZ

do i=1,#rcm

roh=rcm(i)

{multi;config;wf,8,4,2;dm}
emulti_gs(i)=energy(1)
ci
eci_gs(i)=energy(1)
eci_gs_david(i)=energd(1)

end do

table,rcm,emulti_gs,eci_gs,eci_gs_david
Title,Results for OH+ dissociation 3Sig- state

{pop;individual;density,2140.2,charge,state=1.4}

Input file for O-atom
----------------------------------
***,o
print,orbitals,civector

geometry={                                                                      !geometry specification, using z-matrix
o
}

basis=cc-pVQZ


{multi;wf,8,4,2;dm}
ci

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