[molpro-user] Energy in MRCI-F12 calculation

[Lee E.P.F.]

Dear All,

I have posted similar problems early this year and the email exchanges are as given below. I have not got any reply, after my last email to Joachim. 

Regards,
Edmond Lee

*****
Dear Joachim,

I am running a MRCI-F12 calculation using molpro Version 2012.1 linked 5. In the output, I have

 Cluster corrected energies          -739.94638902 (Davidson, fixed reference)
 Cluster corrected energies          -739.94622554 (Davidson, relaxed reference)

When I set (after mrci-f12)

 E_mrf12d=energd;

I get

 SETTING E_MRF12D       =      -739.94634281  AU

This energd value is close to the fixed reference value, but not the same.

My input is as follows:

***,  HPS X1A' cas/mr-f12/cc-pCVQZ-F12
! {mrci-f12;GEM_BETA=1.5;core=2}; only frozen S and P 1s2
! basis=CVQZ-F12; the rest default
! casscf default core/closed; mrci-f12;core,2;
! at optd geom

memory,750,m

geometry={ang;
h;
p,h,ph;
s,p,ps,h,hps;}

ph=1.42096967
ps=1.92641045
hps=102.15989210

gprint,orbitals;

basis=CVQZ-F12

{hf;
occ,13,3;
wf,32,1,0}

{multi;
wf,32,1,0;
natorb,print,ci;}
E_cas=energy

{mrci-f12,GEM_BETA=1.5;
core,2;}

E_mrf12=energy;
E_mrf12d=energd;

table,ph,ps,hps,E_cas,E_mrf12,E_mrf12d;
save,hps_a_mrf12.tab;

---

eof

I am doing energy scans, and all results are similar that the energd values are different from both the fixed and relaxed values.

Many thanks for your attention.

Best Regards,
Edmond

________________________________________
From: Hans-Joachim Werner [werner at theochem.uni-stuttgart.de]
Sent: 12 January 2014 18:07
To: Lee E.P.F.
Subject: Re: [molpro-user] energd in MRCI-F12 caln

Dear Edmond,
Can you please send an example? For me energd=enerd0 in simple test jobs, e.g. for 2 states H2O:

geometry={o;h1,o,r;h2,o,r,h1,theta}
r=1 ang
theta=105

hf
{multi;wf,sym=1;state,2}
{mrci;wf,sym=1;state,2}
show energd*


 ENERGD(1:2)      = [     -76.24065883   -75.85587489] AU
 _ENERGD0(1:2)    = [     -76.24065883   -75.85587489] AU
 _ENERGD1(1:2)    = [     -76.24088239   -75.85608681] AU
 _ENERGD2(1:2)    = [     -76.24079593   -75.85598199] AU
 _ENERGD3(1:2)    = [     -76.24066801   -75.85586566] AU
 _ENERGD4(1:2)    = [     -76.24080525   -75.85597263] AU

Best regards
Joachim

--
Prof. Dr. Hans-Joachim Werner
Institute for Theoretical Chemistry
University of Stuttgart
Pfaffenwaldring 55
D-70569 Stuttgart, Germany
Tel.: (0049) 711 / 685 64400
Fax.: (0049) 711 / 685 64442
e-mail: werner at theochem.uni-stuttgart.de




Am 09.01.2014 um 12:31 schrieb Lee E.P.F. <E.P.Lee at soton.ac.uk>:

> Dear MOLPRO users,
>
> According to the manual:
>
> ENERGD(istate)
>    Total energy for state istate including Davidson correction (set only in CI).
>
> With molpro2012, the Davidson correction now has several cluster corrections (online manual 20.7 Cluster corrections for multi-state MRCI). Which cluster correction does energd refer to now ? Although the manual says that
>
> By default, ENERGD(n)=ENERGD0(n).
>
> and energd0 should be the relaxed value (Table 9 in the manual), but using energd gives neither the fixed nor relaxed value.
>
> Regards,
> Edmond Lee
>
>
>
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