GASCI hamiltonian non-hermicity

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Jakub Visnak

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Mar 24, 2018, 6:41:53 PM3/24/18
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Dear Dirac Experts,


I attempted GAS-CI calculation for non-symmetric geometry of UO2(H2O)5(2+) (*), with SORECP and def-TZVPP basis. The output (attached) ends with

"(GASCIP_RCISTD) Anti-hermiticity of reduced Hamiltonian (real,imag) 3.821D+00 3.036D+00

 FATAL ERROR, this is greater than threshold 1.000D-09"

Aside to the attached CAS(6,7), I have tried CAS(6,9) and CAS(12,12)  (thank you very much Kirk, the fall was due to the memory requirements, with  --mw=12000 --aw=15000 and 125GB in PBS script it works.) 
Except it subsequently falls on abov mentioned anti-hermicity after the first CI iteration, unfortunately (as in CAS(6,7) and CAS(6,9) cases).

I have tried to disable the two-electron integral screening as I supposed that the anti-hermicity must be some numerical artifact (?), but it didn't work. What should I do, please?

For D5h geometry (represented as C2v **) GAS-CI calculation worked for me (with different orbital spaces, more general than CAS, however)


Best regards,
Jakub Visnak





(*)  a cut from spin-free lowest-lying excited state geometry optimization started from a CMD snaphost geometry, presence of point-charges in optimization part gives C1 point group geometry

** from a ground state spin-free ECP/B3LYP geometry optimization in Vacuo
HF_UO2w5dz.out

Nike Dattani

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Mar 24, 2018, 7:38:42 PM3/24/18
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Dear Jakub,
Interesting. Have you had success with a smaller basis set?
With best wishes,
Nike

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Visscher, L.

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Mar 27, 2018, 2:58:01 AM3/27/18
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Dear Jakun,

This looks like a bug that one of the CI developers should have a look at. I'll post this also on our developer list and see whether somebody has time to take a closer look. I'm insufficiently familiar with the GASCIP module to say offhand what is causing the problem and whether there is a work-around for the current release.

best reagrds,

Luuk


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<HF_UO2w5dz.out>

jvi...@gmail.com

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Apr 29, 2021, 10:10:57 PMApr 29
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Dear  Dirac Experts, 

now I have faced the same error message for C1* geometry of NUHFI molecule
 computationals: double-zeta basis set,  4c-CASCI(4,4)   (with GASCIP, as LUCIAREL is not implemented yet for C1*)

The error is " Master node : --- SEVERE ERROR, PROGRAM WILL BE ABORTED ---

 Date and time (Linux) : Sun Apr 25 13:59:33 2021
 Anti-hermiticity of red. Ham. > threshold

 Traceback from this point (gascip_rcistd_+0x3b81): 7 frames.

  6   function name:            gascip_rcistd_+0x3b81
  5   function name:                     rcist_+0x2ad
  4   function name:                   roptst_+0x1ef2
  3   function name:                 krci_calc_+0xade
  2   function name:                     dirac_+0xec4
  1   function name:                     MAIN__+0x7e8
  0   function name:                        main+0x2e"

what should be the work-around, please?
Do you think that FCIDUMP/MO_integrals might be affected by the same bug for the C1* geometries? 
Because the integrals we obtained does not lead to reasonable DMRG energies (lower than reasonable by several orders of magnitude).



Best regards,
Jakub

P.S.: Dear Luuk, did you obtain any information from the Developers on this topic, please?
P.S.II:  This molecule has been already investigated in an article  [1], including 4c-CCSD. 

[1] Wormit M., Olejniczak M., Deppenmeier A-L., Borschevsky A., Saue T., Schwerdtfeger: Strong enhancement of parity violation effects in chiral uranium compounds, Phys. Chem. Chem. Phys., 2014, 16, 17043, DOI:10.1039/c4cp01904k

jvi...@gmail.com

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Apr 29, 2021, 10:17:50 PMApr 29
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For some reasons, attaching files does not work for me here, so I will cut out inputs for SCF run:

inp.inp:
"**DIRAC
.TITLE
 NUHFI molecule, SCF try, DZ basis, 81 electronic pairs total, 13 valence pairs (including two pi)
.WAVE FUNCTION
.ANALYZE
**INTEGRALS
#*TWOINT
#.SCREEN
#-1.0D-14
*READIN
#.UNCONTRACT
**HAMILTONIAN
#.DOSSSS
**WAVE FUNCTION
.SCF
.RESOLVE
.KR CI
#.MP2 NO
*SCF
.ERGCNV
 5.D-11
.MAXITR
 800
.LSHIFT
 0.8
.2NDOPT
*RESOLVE
*KRMCSCF
.INACTIVE
75
.GAS SHELLS
1
12 12 / 12
.CI PROGRAM
LUCIAREL
.MAX MACRO
 200
*KRCICALC
.CI PROGRAM
GASCIP
#.FCIDUMP
.CIROOTS
 1 4
.MAX CI
 1000
.INACTIVE
 75
.GAS SHELLS
 1
 12 12 / 12
.MXCIVE
 20
#.OMEGAQ
.ANALYZ
#*MP2 NO
#.ACTIVE
#6..150
#.MULPOP
#active
**MOLECULE
**GENERAL
.ACMOUT
.PCMOUT
**ANALYZE
.PRIVEC
.MULPOP
#.PROJECTION
*PRIVEC
.VECPRI
all
.PRICMP
 1 1
*MULPOP
.VECPOP
all
#*PROJECTION
#.VECPRJ
#all
##.VECREF
##2
##AFTHXX
##1
##all
##AFCOXX
##2
##all
##.OWNBAS
#.ATOMS
#AFTHCX
#all
#AFCXXX
#all
#AFOXXX
#all
##.PROTHR
##-1.0D-4
#.POLREF
*END OF INPUT
"
mol.mol:
"DIRAC
NUHFI, C1 geometry (the second zero), ca. equilibrium geometry
there are 5 kinds of atoms (N,U,H,F,I), 0 total charge (the first zero), Angstroem, "A" should be on the exact 20th position
C   5  0 0         A
        7.    1
N     0.5255468   0.2608732    2.0653705
LARGE BASIS cc-pVDZ
       92.    1
U    -0.0303969  -0.0391832    0.4766824
LARGE BASIS dyall.v2z
        1.    1
H     1.5796088  -0.1407848   -0.6453847
LARGE BASIS cc-pVDZ
        9.    1
F    -0.9339928  -1.1591900   -0.9135786
LARGE BASIS cc-pVDZ
       53.    1
I    -0.7699855   2.4435462   -0.8140155
LARGE BASIS dyall.v2z
FINISH
"
directive (Dirac 17):
pam-dirac --scratch=$SCRATCHDIR/Dscr --noarch --gb=47 --ag=48 --inp=inp.inp --mol=mol.mol --outcmo --get="DFCOEF DFPCMO DFACMO"

and separate CI(4,4) run done after it (starting from the converged DHF orbitals):

inp.inp:
"**DIRAC
.TITLE
 NUHFI molecule, SCF try, DZ basis, 81 electronic pairs total, 13 valence pairs (including two pi)
.WAVE FUNCTION
.ANALYZE
**INTEGRALS
#*TWOINT
#.SCREEN
#-1.0D-14
*READIN
#.UNCONTRACT
**HAMILTONIAN
#.DOSSSS
**WAVE FUNCTION
#.SCF
#.RESOLVE
.KR CI
#*SCF
#.ERGCNV
# 5.D-11
#.MAXITR
# 800
#.LSHIFT
# 0.8
#.2NDOPT
#*RESOLVE
*KRCICALC
.CI PROGRAM
GASCIP
#.FCIDUMP
.CIROOTS
 1 4
.MAX CI
 1000
.INACTIVE
 79
.GAS SHELLS
 1
 4 4 / 4
.MXCIVE
 20
#.OMEGAQ
.ANALYZ
#*MP2 NO
#.ACTIVE
#6..150
#.MULPOP
#active
**MOLECULE
**GENERAL
.ACMOUT
.PCMOUT
**ANALYZE
.PRIVEC
.MULPOP
#.PROJECTION
*PRIVEC
.VECPRI
all
.PRICMP
 1 1
*MULPOP
.VECPOP
all
#*PROJECTION
#.VECPRJ
#all
##.VECREF
##2
##AFTHXX
##1
##all
##AFCOXX
##2
##all
##.OWNBAS
#.ATOMS
#AFTHCX
#all
#AFCXXX
#all
#AFOXXX
#all
##.PROTHR
##-1.0D-4
#.POLREF
*END OF INPUT
"
mol.mol:
the same
directive:
pam-dirac --scratch=$SCRATCHDIR/Dscr --noarch --gb=47 --ag=48 --inp=inp.inp --put="DFCOEF DFPCMO DFACMO" --incmo --mol=mol.mol --outcmo --get="DFCOEF DFPCMO DFACMO"



Knecht Stefan

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May 4, 2021, 5:58:11 PMMay 4
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Dear Jakub,

thanks for the inputs. I am currently looking into this issue but even with the DZ basis sets the calculations take some time. 
For the ground state I am getting a reference KRCI energy for the CAS(4,4) case of 
-35329.57894973 Hartree 
Does that make sense to you?

with best regards
Stefan

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Knecht Stefan

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May 5, 2021, 4:26:04 PMMay 5
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Dear Jakub,

could you please try the attached FCIDUMP file? My DMRG reference energy is in this case
-35329.5789201008 Hartree
The SCF energy is
-35329.578892973397 Hartree

Note that the SCF/FCI energy is different from the one of my previous mail since I had to run the SCF on my DMRG development branch which still uses an older CODATA set 
for the physical constants (speed of light, …) than the current master/release branch of Dirac. 

with best regards
Stefan

p.s.: as to why the GASCIP sub-space Hamiltonian gets non-Hermitian, I can’t say yet.


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