[molpro-user] Multi with F12?

[Terry Frankcombe]

Hi Kirk, molpro people

I've played around with a number of things, but am yet to get this
working.

The closest I've gotten so far is:

Multi-RHF-CCSD={
  {multi; occ 12; closed 10; WF 22 1 2; accuracy step=0.01; maxiter 40}
  {RHF}
  {RCCSD-F12A,ri_basis=vdz-f12/optri} }

Multi-RHF-CCSD
{OptG,numerical,proc=Multi-RHF-CCSD; inactive R}


The problem is where the orbitals come from and go to.

As I've written it here, the first multi dumps to 2140.2, that's read by
RHF, which dumps to 2100.2, which is read by RCCSD.

When OptG starts multi and RHF read the previous orbitals on 2140.2 and
2100.2, respectively, so I've gained nothing (and the RHF fails during
the stepping for the gradient).

If I specify "orbital 2222.2" for multi and RHF then again it works for
the initial energy, but once OptG gets going the orbitals from multi are
dumped in 2222.1, then the subsequent RHF reads from 2222.2.  Again,
I've gained nothing.  If I try to dump in 2222.1 OptG tells me off and
stops.

If I use "start 2222.1" for the RHF it gets ignored and orbitals are
read from 2222.2 in the OptG.

All this is with 2009.1.  I've attached a copy of the input.  (Yes, in
this system there is a low-lying excited state, which is likely
contributing to my convergence problems.)

If there are any suggestions about how to get this to work, I'll be
happy to hear them.

Regards
Terry



On Thu, 2010-09-23 at 08:25 -0700, Kirk Peterson wrote:
> Hi Terry,
> 
> Sorry about leading you astray, I thought this now worked but I just tried with 2010.2 and it doesn't find the
> Fock matrix data.  The only workaround I can think might work is to use a procedure to carry out your
> energy evaluation and in there directly follow your multi calculation with a regular hf, making sure the latter
> reads the orbitals from multi.
> 
> -Kirk
> 
> On Sep 23, 2010, at 12:19 AM, Terry Frankcombe wrote:
> 
> > On Wed, 2010-09-22 at 08:02 -0700, Kirk Peterson wrote:
> >> Hi Terry,
> >> For using multi for your HF, just invoke multi where you would normally call hf but include
> >> occ and closed cards to restrict it to a single determinant.  Also output the orbitals as type
> >> canonical.  In the rccsd-f12a calculation, specify the record of these orbitals to read in and you might have
> >> to also include a "ignore_error" option on the orbital directive since usually the ccsd(t) code doesn't
> >> like what looks like non-canonical orbitals for the (t) step.
> > 
> > Hi Kirk
> > 
> > Thanks for that.  It looks like I'm getting close, but not there yet.
> > 
> > With 2009.1:
> > 
> > {multi; occ 12; closed 10; WF 22 1 2; canonical 2140.2}
> > {RCCSD-F12A,ri_basis=vdz-f12/optri; orbital 2140.2,canonical}
> > 
> > In the RCCSD I get:
> > 
> > Augmented Hessian optimization of geminal fit. Trust ratio= 0.40000
> > Convergence reached after   2 iterations. Final gradient= 8.43D-16, Step= 4.27D-06, Delta= 1.28D-09
> > 
> > Alpha:                 0.19532     0.81920     2.85917     9.50073    35.69989   197.79328
> > Coeff:                 0.27070     0.30552     0.18297     0.10986     0.06810     0.04224
> > 
> > 
> > 
> > ?ERROR IN READ_DUMP: OCC SET= 1 NOT FOUND IN RECORD    2140.2
> > 
> > THE RECORD CONTAINS THE FOLLOWING MCSCF DATA:
> > ORBITALS/MULTI              SET= 1  STATE=  1.1  MS2=2  NELEC=  2
> > DENSITY/CHARGE              SET= 1  STATE=  1.1  MS2=2  NELEC=  2
> > ORBITALS/CANONICAL          SET= 2  STATE=  1.1  MS2=2  NELEC=  2
> > GROUP/CANONICAL             SET= 1  STATE=  1.1  MS2=2  NELEC=  2
> > OCC/CANONICAL               SET= 2  STATE=  1.1  MS2=2  NELEC=  2
> > EIG/CANONICAL               SET= 2  STATE=  1.1  MS2=2  NELEC=  2
> > 
> > GLOBAL ERROR fehler on processor   0
> > 
> > 
> > 
> > I get the same whether I give the canonical option, the set=2 option, or
> > no option to the orbital directive.
> > 
> > How can I get RCCSD to read some other occupations, or get the
> > occupations into set 2?
> > 
> > Ciao
> > Terry
> > 
> > 
> 
-- 
Dr. Terry Frankcombe
Research School of Chemistry, Australian National University
Ph: (+61) 0417 163 509    Skype: terry.frankcombe
-------------- next part --------------
basis=VDZ-F12
symmetry NoSym
Angstrom
geometry={
 C
 N C rCN
 H C rCH N aHCN
 O C R N aOCN H dNCOH }

R=1.6
rCN=1.23
rCH=1.08
aHCN=132.0
aOCN=114.5
dNCOH=179.98

Multi-RHF-CCSD={
  {multi; occ 12; closed 10; WF 22 1 2; accuracy step=0.01; maxiter 40}
  {RHF}
  {RCCSD-F12A,ri_basis=vdz-f12/optri} }

Multi-RHF-CCSD
{OptG,numerical,proc=Multi-RHF-CCSD; inactive R}