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Pages: 1

#1 2023-01-30 13:38:48

danielreta
Member
Registered: 2020-02-21
Posts: 7

RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

Hi,

I want to obtain the zero-field splitting parameters of a Mn(II) compound at a CASPT2 level.

I have run the RASSCF for the ground S=6 root and the 24 roots of the S=4 manifold  and subsequently CASPT2 for S=4 is run for the lowest 17 roots only. Then I run RASSI pointing to the corresponding two IPH files - the energies for the S=4 roots are the CASPT2 ones, while that for the S=6 root is that of the CASSCF, which is not what I want. The input is 

&RASSCF
 FileOrb= 1.RasOrb
 Spin= 6
 Charge= 0
 CiRoot= 1 1 1
 ORBA= FULL
 MAXORB= 1
 Nactel= 5 0 0
 RAS2= 5
>> COPY $Project.JobIph 1_IPH
>> COPY $Project.RasOrb 1.RasOrb
>> COPY $Project.rasscf.h5 1.rasscf.h5

&CASPT2  &END
 Title
 caspt2 for the ground state high-spin sextet
 Frozen
 50
 End  of  input
>> COPY $Project.JobIph 1PT2_IPH

&RASSCF
 FileOrb= 2.RasOrb
 Spin= 4
 Charge= 0
 CiRoot= 24 24 1
 ORBA= FULL
 MAXORB= 24
 Nactel= 5 0 0
 RAS2= 5
>> COPY $Project.JobIph 2_IPH
>> COPY $Project.RasOrb 2.RasOrb
>> COPY $Project.rasscf.h5 2.rasscf.h5

&CASPT2  &END
 Title
  mscaspt2 for the 17 lowest-lying roots of the spin quartet multiplet
 Frozen
  50
 MultiState
  17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
 End  of  input
 >> COPY $Project.JobIph 2PT2_IPH

&RASSI
  SPIN
  MEES
  HEFF
  EPRG= 7.0D-1
  Nr of JobIph= 2 1 17
  1
  1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
  IPHN
  1PT2_IPH
  2PT2_IPH
  PROP
  3
  'ANGMOM' 1
  'ANGMOM' 2
  'ANGMOM' 3

&SINGLE_ANISO
  MLTP= 1; 6
  QUAX= 1

I also tried passing the CASPT2 energies via the HDIAG keyword, but it did not work either.

Does anyone know how to fix this?

Thanks

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#2 2023-01-30 13:51:29

Ignacio
Administrator
From: Uppsala
Registered: 2015-11-03
Posts: 1,012

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

Try passing the JOBMIX files instead of JOBIPH, and add EJOB to RASSI

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#3 2023-01-30 13:58:07

danielreta
Member
Registered: 2020-02-21
Posts: 7

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

I did not save the JOBMIX files... I need to repeat one of the CASPT2 sections then. I guess there is no other option?

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#4 2023-01-30 14:49:25

Ignacio
Administrator
From: Uppsala
Registered: 2015-11-03
Posts: 1,012

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

If you have the $Project.caspt2.h5 files, try with them (but without EJOB in that case).

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#5 2023-01-30 16:49:10

danielreta
Member
Registered: 2020-02-21
Posts: 7

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

No, I don't... The job should be done by tomorrow and I'll be able to check, thanks

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#6 2023-01-31 10:39:03

danielreta
Member
Registered: 2020-02-21
Posts: 7

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

Hi. It doesnt seem to have worked. This is a summary of the energies

S=6 root   |    RASSCF root  1  -2847.96595377    |    CASPT2 Root  1  -2852.39956228     |    RASSI State    1      0.00000000

S=4 roots |    RASSCF root  1  -2847.83604544     |    CASPT2 Root  1  -2852.28861695     |    RASSI State    2  -2852.29240452
   "           |    RASSCF root  2  -2847.83543096     |    CASPT2 Root  2  -2852.28922489     |    RASSI State    3  -2852.29233670
   "           |    RASSCF root  3  -2847.83507952     |    CASPT2 Root  3  -2852.29190332     |    RASSI State    4  -2852.29089348
   "           |    RASSCF root  4  -2847.83397319     |    CASPT2 Root  4  -2852.29055854     |    RASSI State    5  -2852.29003402
   "           |    RASSCF root  5  -2847.83212023     |    CASPT2 Root  5  -2852.29188780     |    RASSI State    6  -2852.28934670
   "           |    RASSCF root  6  -2847.82931146     |    CASPT2 Root  6  -2852.28899352     |    RASSI State    7  -2852.28928852
   "           |    RASSCF root  7  -2847.82912887     |    CASPT2 Root  7  -2852.28874381     |    RASSI State    8  -2852.28838489
   "           |    RASSCF root  8  -2847.82698481     |    CASPT2 Root  8  -2852.28785550     |    RASSI State    9  -2852.28798435
   "           |    RASSCF root  9  -2847.82691971     |    CASPT2 Root  9  -2852.28765373     |    RASSI State   10  -2852.28760814
   "           |    RASSCF root 10  -2847.81264203    |    CASPT2 Root 10  -2852.27661701    |    RASSI State   11  -2852.27640539
   "           |    RASSCF root 11  -2847.81148670    |    CASPT2 Root 11  -2852.27474792    |    RASSI State   12  -2852.27438828
   "           |    RASSCF root 12  -2847.80640317    |    CASPT2 Root 12  -2852.27066116    |    RASSI State   13  -2852.27061674
   "           |    RASSCF root 13  -2847.80445826    |    CASPT2 Root 13  -2852.26905564    |    RASSI State   14  -2852.26862894
   "           |    RASSCF root 14  -2847.80404207    |    CASPT2 Root 14  -2852.26776097    |    RASSI State   15  -2852.26719099
   "           |    RASSCF root 15  -2847.79546817    |    CASPT2 Root 15  -2852.26409016    |    RASSI State   16  -2852.26390068
   "           |    RASSCF root 16  -2847.78633866    |    CASPT2 Root 16  -2852.25608261    |    RASSI State   17  -2852.25550864
   "           |    RASSCF root 17  -2847.78487349    |    CASPT2 Root 17  -2852.25439518    |    RASSI State   18  -2852.25392774
   "           |    RASSCF root 18  -2847.73546293
   "           |    RASSCF root 19  -2847.73511225
   "           |    RASSCF root 20  -2847.73363316
   "           |    RASSCF root 21  -2847.73288096
   "           |    RASSCF root 22  -2847.73225356
   "           |    RASSCF root 23  -2847.73074586
   "           |    RASSCF root 24  -2847.73036880

and this is the input for RASSI I used

&RASSI
  SPIN
  MEES
* When reading JOBMIX files, use EJob. HEFF prevents recalculation of spin-free Hamiltonian
  EJob
  HEFF
  EPRG= 7.0D-1
  Nr of JobIph= 2 1 17
  1
  1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
  IPHN
  1PT2_MIX
  2PT2_MIX
  PROP
  3
  'ANGMOM' 1
  'ANGMOM' 2
  'ANGMOM' 3

where 1PT2_MIX and 2PT2_MIX have been saved with >> COPY $Project.JobMix 1PT2_MIX and >> COPY $Project.JobMix 2PT2_MIX after the corresponding CASPT2 section.

Last edited by danielreta (2023-01-31 10:40:20)

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#7 2023-01-31 14:05:00

Ignacio
Administrator
From: Uppsala
Registered: 2015-11-03
Posts: 1,012

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

I'd suggest you try a smaller/simpler test case and add the complexity later. This seems to work for me:

&GATEWAY
  Coord = 1

    Mn 0.0 0.0 0.0
  Group = NoSymm
  Basis = ANO-RCC-VDZP
  RICD

&SEWARD

&RASSCF
  Spin = 6
  Charge = 0
  NactEl = 5
  RAS2 = 5
  CIRoot = 1 1 1
> COPY $Project.JobIph 1_IPH

&CASPT2
> COPY $Project.JobMix 1PT2_MIX

&RASSCF
  FileOrb = $Project.rasscf.h5
  Spin = 4
  Charge = 0
  NactEl = 5
  RAS2 = 5
  CIRoot = 12 12 1
> COPY $Project.JobIph 2_IPH

&CASPT2
  Multistate = 9
    1 2 3 4 5 6 7 8 9
> COPY $Project.JobMix 2PT2_MIX

&RASSI
  NrOfJob = 2 all
  IphNames
    1PT2_MIX
    2PT2_MIX
  EJob
  SpinOrbit

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#8 2023-02-01 14:30:35

danielreta
Member
Registered: 2020-02-21
Posts: 7

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

Thanks. I have tried your example. Now, the RASSI energy for the S=6 state is the CASPT2 one, but those for the S=4 are neither the RASSCF nor the CASPT2 ones - if you take the energy differences between the CASPT2 roots and the RASSI ones there is variation

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#9 2023-02-01 15:56:39

Ignacio
Administrator
From: Uppsala
Registered: 2015-11-03
Posts: 1,012

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

They are the MS-CASPT2 energies, and the corresponding H matrix is diagonal (because the CASSCF states have already been mixed). That should be equivalent to reading the full SS-CASPT2 H matrix.

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#10 2023-02-01 16:12:36

danielreta
Member
Registered: 2020-02-21
Posts: 7

Re: RASSI on CASPT2 - HEFF reads RASSCF energies for SS-CASPT2

oh! My bad! Ok, that makes sense then.
So in summary, if one reads from the JobMix and uses EJOB, it works. Thanks

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