Author Topic: Heavy elements and relativistic effects  (Read 4174 times)

JakubV

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Heavy elements and relativistic effects
« on: April 05, 2021, 03:44:19 PM »
Dear Turbomole Users,

first I would like to apologize if this question was already asked in any variant or is easy to find an answer in the Reference book to TM.

I wonder about possibilities to reach the edge of the periodic table of elements (or to go slightly over) in Turbomole.
I see in TM 7.1 which I have now easy access to in "basen" files the heaviest element supported is Lr with Z = 103.

But I would wish to use TM 7.1 for example for NSgHFI chiral molecule optimization. What is the best way to do that?
I would be ok with scalar quasirelativistic calculation with some ECP and basis set found elsewhere in the literature (spin-orbit 2c-ECP are in general also supported, so that might be another step)

Maybe I could import them under file "sg" into basen directory and just run TM, but will be that element label recognized?
Or I will have to define the molecule with, let's say "Lr", important Seaborgium basis set under a new name to "lr" file in basen and change proton number of given atom (labelled "Lr") to Z = 106 (as Seaborgium has) and also change the number of electrons to get desired electroneutral molecule.

Could you recommend some better way or comment on the limits of TM with reaching superheavy elements? I suppose that for even heavier elements, quasirelativistic methods might be less accurate and I should use DHK.

Best regards,
JakubV
« Last Edit: April 18, 2021, 01:54:32 AM by JakubV »

JakubV

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Relativistic effects, Kramers unrestricted
« Reply #1 on: March 18, 2023, 02:27:40 AM »
Dear Turbomole Experts,

I would like to investigate molecules like UH+ (or neutral UH), which have several open shells (4 or 5 in scalar treatment), also with spin-orbit splitting included and possibly at the DFT level.

Combining UHF and spin-orbit (soghf) - is it somehow possible, please? As that would mean - Kramers unrestricted SCF/DFT...
Is there any Kramers unrestricted method in Turbomole, or could you hint to me software capable of that, please?

ROHF and soghf shall be possible to combine, but (possibly also since DFT is not well defined for ROHF) TM will not allow me to combine ROHF and DFT anyway.

Best regards,
JakubV

P.S.:  I apologise if it is somehow clear from the documentation.

JakubV

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Re: Heavy elements and relativistic effects
« Reply #2 on: March 18, 2023, 10:07:41 PM »
P.S. II: So I have tried the ROHF + soghf and faced this error.
How can I work around this, please?

Code: [Select]
              RI-J - INFORMATION
           ------------------------
 Contributions to RI integral batches:
  neglected integral batches:                     0
  direct contribution:                            0
  memory contribution:                   561
 Memory core needed for (P|Q) and Cholesky      1 MByte
 Memory core minimum needed except of (P|Q)     1 MByte
 Total minimum memory core needed (sum)         1 MByte

 ****************************************
 Memory allocated for RI-J    34 MByte
 ****************************************


 Difference densities switched on

 Exact HF-exchange is used

 Starting SCF iterations


 ITERATION  ENERGY          1e-ENERGY        2e-ENERGY     NORM[dD(SAO)]  TOL
     1  -484.39648956847    -782.13430779     289.39910750    0.000D+00 0.203D-11
                            Ex   [ex-K]  = -49.5291743869
                            Coul [RI-J]   =  338.928281885
                            E[SO]        =  0.00000000000
Subroutine ddmat can not establish optimal linear combination of delta densities !
 Next fock matrix will be calculated from scratch !
Subroutine ddmat can not establish optimal linear combination of delta densities !
 Next fock matrix will be calculated from scratch !
                                              current damping :  2.000

 ITERATION  ENERGY          1e-ENERGY        2e-ENERGY     NORM[dD(SAO)]  TOL
     2                   NaN              NaN              NaN0.000D+00 0.203D-11
                            Ex   [ex-K]  =                NaN
                            Coul [RI-J]   =                NaN
                            E[SO]        =                NaN
Subroutine ddmat can not establish optimal linear combination of delta densities !
 Next fock matrix will be calculated from scratch !
Subroutine ddmat can not establish optimal linear combination of delta densities !
 Next fock matrix will be calculated from scratch !
                                              current damping :  2.050

 ITERATION  ENERGY          1e-ENERGY        2e-ENERGY     NORM[dD(SAO)]  TOL
     3                   NaN              NaN              NaN0.000D+00 0.203D-11
                            Ex   [ex-K]  =                NaN
                            Coul [RI-J]   =                NaN
                            E[SO]        =                NaN
Subroutine ddmat can not establish optimal linear combination of delta densities !
 Next fock matrix will be calculated from scratch !
Subroutine ddmat can not establish optimal linear combination of delta densities !
 Next fock matrix will be calculated from scratch !
                                              current damping :  2.100
... and so on, there are only NaNs onward.

control file
Code: [Select]
$title
$symmetry c1
$user-defined bonds    file=coord
$coord    file=coord
$optimize
 internal   off
 redundant  off
 cartesian  on
 global     off
 basis      off
$atoms
u  1                                                                           \
   basis =u Cao-2c                                                             \
   ecp   =u def-ecp-2c                                                         \
   jbas  =u def-TZVPP
h  2                                                                           \
   basis =h aug-cc-pVTZ-2c                                                     \
   jbas  =h universal
$basis    file=basis
$ecp    file=basis
$scfmo   file=mos
$closed shells
 a       1-14                                   ( 2 )
$scfiterlimit     8000
$scfconv        8
$thize     0.10000000E-04
$thime        5
$scfdamp   start=2.000  step=0.050  min=0.50
$scfdump
$scfintunit
 unit=30       size=0        file=twoint
$scfdiis
$maxcor    500 MiB  per_core
$scforbitalshift  closedshell=.4
$drvopt
   cartesian  on
   basis      off
   global     off
   hessian    on
   dipole     on
   nuclear polarizability
$interconversion  off
   qconv=1.d-7
   maxiter=25
$coordinateupdate
   dqmax=0.3
   interpolate  on
   statistics    5
$forceupdate
   ahlrichs numgeo=0  mingeo=3 maxgeo=4 modus=<g|dq> dynamic fail=0.3
   threig=0.005  reseig=0.005  thrbig=3.0  scale=1.00  damping=0.0
$forceinit on
   diag=default
$energy    file=energy
$grad    file=gradient
$forceapprox    file=forceapprox
$soghf
$ricore      800
$rij
$jbas    file=auxbasis
$rundimensions
   natoms=2
   nbf(CAO)=164
   nbf(AO)=127
$last step     ridft
$charge from ridft
            NaN (not to be modified here)
$dipole from ridft
  x                  NaN    y                  NaN    z                  NaN    a.u.
   | dipole | =             NaN  debye
$spinor_real       file=spinor.r
$spinor_imag       file=spinor.i
$spinor shells
 a       1-14                                   ( 2 )
 a       19-20                                  ( 1 )
$end

coord
Code: [Select]
$coord
    0.00000000000000      0.00000000000000     -1.91876184798602      u
    0.00000000000000      0.00000000000000      1.91876184798602      h
$user-defined bonds
$end

uwe

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Re: Heavy elements and relativistic effects
« Reply #3 on: April 05, 2023, 07:35:02 PM »
Hello,

the basis sets and the ECP you have named in the control file are not part of the default library in Turbomole, so I guess you have added them manually. In order to reproduce your results (or non-results), please post the files basis and auxbasis too.

Using basis sets that are ready to use, the calculation runs without NaN. And results in a very high spin-orbit energy: E[SO]        = -1.4512173 (Hartree).

JakubV

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Re: Heavy elements and relativistic effects
« Reply #4 on: April 10, 2023, 03:46:15 AM »
Hello,

Thank you.

basis:
Code: [Select]
$basis
*
u Cao-2c
# u     (84s78p50d32f18g) / [6s6p5d4f3g]
# {(14)(14)(14)(14)(14)(14)/(13)(13)(13)(13)(13)(13)/*****/8888/666}
*
  14  s
  29520.834000      0.44000000000E-04
  4449.8874000      0.32000000000E-03
  1018.7754000      0.13950000000E-02
  289.53480000      0.28140000000E-02
  46.999000000      0.96435000000E-01
  33.570700000     -0.48796700000
  23.979100000      0.80750800000
  10.144100000      -1.1275040000
  2.7658000000       1.0605270000
  1.4570000000      0.40029200000
 0.61510000000      0.16450000000E-01
 0.27800000000     -0.21900000000E-03
 0.57000000000E-01 -0.42000000000E-04
 0.23300000000E-01 -0.17600000000E-03
  14  s
  29520.834000     -0.33000000000E-04
  4449.8874000     -0.25200000000E-03
  1018.7754000     -0.10150000000E-02
  289.53480000     -0.24150000000E-02
  46.999000000     -0.39561000000E-01
  33.570700000      0.21883100000
  23.979100000     -0.39799000000
  10.144100000      0.66473800000
  2.7658000000      -1.0134180000
  1.4570000000     -0.39336500000
 0.61510000000      0.90434400000
 0.27800000000      0.51802200000
 0.57000000000E-01  0.73065000000E-01
 0.23300000000E-01  0.29494000000E-01
  14  s
  29520.834000      0.14000000000E-04
  4449.8874000      0.10300000000E-03
  1018.7754000      0.41100000000E-03
  289.53480000      0.10040000000E-02
  46.999000000      0.14267000000E-01
  33.570700000     -0.81043000000E-01
  23.979100000      0.15071500000
  10.144100000     -0.25976600000
  2.7658000000      0.42077500000
  1.4570000000      0.18936800000
 0.61510000000     -0.54000500000
 0.27800000000     -0.41236800000
 0.57000000000E-01  0.78498300000
 0.23300000000E-01  0.42418900000
  14  s
  29520.834000     -0.40000000000E-04
  4449.8874000     -0.29800000000E-03
  1018.7754000     -0.12590000000E-02
  289.53480000     -0.27750000000E-02
  46.999000000     -0.50598000000E-01
  33.570700000      0.25346600000
  23.979100000     -0.44023800000
  10.144100000      0.74525300000
  2.7658000000      -1.6001180000
  1.4570000000      0.10942500000
 0.61510000000       2.8676280000
 0.27800000000      -2.2405680000
 0.57000000000E-01 -0.56479900000
 0.23300000000E-01   1.0052220000
  14  s
  29520.834000     -0.52000000000E-04
  4449.8874000     -0.33900000000E-03
  1018.7754000     -0.17490000000E-02
  289.53480000     -0.25740000000E-02
  46.999000000     -0.11400200000
  33.570700000      0.46060100000
  23.979100000     -0.66738200000
  10.144100000      0.97360400000
  2.7658000000      -2.8663060000
  1.4570000000       2.6371450000
 0.61510000000      0.78197100000
 0.27800000000      -2.3309880000
 0.57000000000E-01   2.7379670000
 0.23300000000E-01  -1.9581840000
  14  s
  29520.834000     -0.10600000000E-03
  4449.8874000     -0.79000000000E-03
  1018.7754000     -0.32630000000E-02
  289.53480000     -0.75280000000E-02
  46.999000000     -0.96221000000E-01
  33.570700000      0.48533100000
  23.979100000     -0.88253300000
  10.144100000       1.7272160000
  2.7658000000      -7.3348920000
  1.4570000000       11.247552000
 0.61510000000      -9.1077550000
 0.27800000000       4.8075400000
 0.57000000000E-01  -1.8377640000
 0.23300000000E-01  0.96683800000
  13  p
  499.74880000      0.21900000000E-03
  114.01920000      0.11900000000E-02
  21.908800000     -0.42782000000E-01
  15.649200000      0.32435300000
  11.178000000     -0.51152900000
  7.9843000000     -0.71299000000E-01
  3.1325000000      0.70400800000
  1.6077000000      0.46506100000
 0.70610000000      0.54229000000E-01
 0.32290000000     -0.18190000000E-02
 0.13290000000      0.23020000000E-02
 0.80000000000E-01 -0.11290000000E-02
 0.27100000000E-01  0.14300000000E-03
  13  p
  499.74880000     -0.12700000000E-03
  114.01920000     -0.64300000000E-03
  21.908800000      0.18120000000E-01
  15.649200000     -0.16645300000
  11.178000000      0.30681100000
  7.9843000000     -0.14845000000E-01
  3.1325000000     -0.47692400000
  1.6077000000     -0.27661200000
 0.70610000000      0.48090800000
 0.32290000000      0.61554300000
 0.13290000000      0.15832400000
 0.80000000000E-01 -0.53580000000E-02
 0.27100000000E-01  0.33480000000E-02
  13  p
  499.74880000      0.10300000000E-03
  114.01920000      0.47300000000E-03
  21.908800000     -0.11387000000E-01
  15.649200000      0.12193000000
  11.178000000     -0.23477600000
  7.9843000000      0.11640000000E-01
  3.1325000000      0.40892800000
  1.6077000000      0.24097800000
 0.70610000000     -0.88849900000
 0.32290000000     -0.81066000000E-01
 0.13290000000      0.35041600000
 0.80000000000E-01  0.61336800000
 0.27100000000E-01  0.14449700000
  13  p
  499.74880000     -0.21900000000E-03
  114.01920000     -0.35300000000E-03
  21.908800000     -0.18092000000E-01
  15.649200000     -0.55835000000E-01
  11.178000000      0.15768400000
  7.9843000000      0.14030500000
  3.1325000000     -0.90751400000
  1.6077000000      0.13107000000E-01
 0.70610000000       1.8114410000
 0.32290000000      -1.3721130000
 0.13290000000      -1.0744100000
 0.80000000000E-01   1.2968810000
 0.27100000000E-01  0.24976800000
  13  p
  499.74880000     -0.59500000000E-03
  114.01920000      0.12460000000E-02
  21.908800000     -0.19571600000
  15.649200000      0.55935700000
  11.178000000     -0.77562600000
  7.9843000000      0.96811100000
  3.1325000000      -2.6806830000
  1.6077000000       2.9400860000
 0.70610000000     -0.33325500000
 0.32290000000      -2.2023430000
 0.13290000000       3.5265940000
 0.80000000000E-01  -1.9100030000
 0.27100000000E-01 -0.25671600000
  13  p
  499.74880000      0.33800000000E-03
  114.01920000      0.20000000000E-02
  21.908800000     -0.62289000000E-01
  15.649200000      0.60381600000
  11.178000000      -1.3925220000
  7.9843000000      0.60888500000
  3.1325000000       2.9334310000
  1.6077000000      -5.4696850000
 0.70610000000       5.8830580000
 0.32290000000      -4.8762900000
 0.13290000000       3.1419660000
 0.80000000000E-01 -0.90361600000
 0.27100000000E-01 -0.50458500000
  10  d
  258.15240000      0.13600000000E-03
  75.170300000      0.10760000000E-02
  20.786900000      0.12136000000E-01
  7.6295000000     -0.22992100000
  5.5167000000      0.27823100000
  2.6058000000      0.55197500000
  1.2781000000      0.37784400000
 0.56170000000      0.74069000000E-01
 0.21350000000      0.82000000000E-04
 0.71900000000E-01  0.48400000000E-03
  10  d
  258.15240000     -0.42000000000E-04
  75.170300000     -0.45000000000E-03
  20.786900000     -0.39390000000E-02
  7.6295000000      0.84412000000E-01
  5.5167000000     -0.11345600000
  2.6058000000     -0.21327000000
  1.2781000000     -0.10072200000
 0.56170000000      0.32178300000
 0.21350000000      0.56163900000
 0.71900000000E-01  0.34499100000
  10  d
  258.15240000     -0.27000000000E-04
  75.170300000     -0.10450000000E-02
  20.786900000     -0.47600000000E-02
  7.6295000000      0.12809600000
  5.5167000000     -0.16296400000
  2.6058000000     -0.46338800000
  1.2781000000     -0.54235000000E-01
 0.56170000000       1.0725750000
 0.21350000000     -0.28144300000
 0.71900000000E-01 -0.60831700000
  10  d
  258.15240000     -0.29300000000E-03
  75.170300000      0.34670000000E-02
  20.786900000     -0.92670000000E-02
  7.6295000000     -0.10746000000E-01
  5.5167000000     -0.60234000000E-01
  2.6058000000       1.2661300000
  1.2781000000      -1.5081050000
 0.56170000000      0.62980000000E-01
 0.21350000000       1.0547380000
 0.71900000000E-01 -0.89879800000
  10  d
  258.15240000     -0.57000000000E-04
  75.170300000     -0.19670000000E-02
  20.786900000     -0.10974000000E-01
  7.6295000000      0.42766800000
  5.5167000000     -0.70833200000
  2.6058000000      -1.0371240000
  1.2781000000       2.6179860000
 0.56170000000      -2.5458260000
 0.21350000000       1.6865530000
 0.71900000000E-01 -0.78735100000
   8  f
  59.366600000      0.14240000000E-02
  20.389000000      0.11120000000E-01
  8.1761000000      0.41970000000E-01
  3.5111000000      0.20773200000
  1.6789000000      0.37075500000
 0.76040000000      0.37377500000
 0.31700000000      0.25299600000
 0.11490000000      0.97955000000E-01
   8  f
  59.366600000     -0.16900000000E-02
  20.389000000     -0.11132000000E-01
  8.1761000000     -0.50308000000E-01
  3.5111000000     -0.22173500000
  1.6789000000     -0.37834000000
 0.76040000000     -0.13232000000E-01
 0.31700000000      0.52509800000
 0.11490000000      0.47337000000
   8  f
  59.366600000     -0.22610000000E-02
  20.389000000     -0.18893000000E-01
  8.1761000000     -0.67853000000E-01
  3.5111000000     -0.41444300000
  1.6789000000     -0.43124600000
 0.76040000000       1.0024230000
 0.31700000000     -0.36904000000E-01
 0.11490000000     -0.61229700000
   8  f
  59.366600000     -0.34700000000E-03
  20.389000000      0.30982000000E-01
  8.1761000000     -0.82130000000E-02
  3.5111000000      0.72130300000
  1.6789000000     -0.46921800000
 0.76040000000     -0.74705300000
 0.31700000000       1.3764810000
 0.11490000000     -0.94418200000
   6  g
  59.366600000      0.10140000000E-02
  20.389000000      0.11848000000E-01
  8.1761000000      0.39302000000E-01
  3.5111000000      0.12419600000
  1.6789000000      0.23387000000
 0.76040000000      0.68487500000
   6  g
  59.366600000      0.35610000000E-02
  20.389000000      0.28234000000E-01
  8.1761000000      0.13727400000
  3.5111000000      0.30428400000
  1.6789000000      0.78734300000
 0.76040000000     -0.90371200000
   6  g
  59.366600000     -0.73300000000E-03
  20.389000000     -0.75550000000E-01
  8.1761000000     -0.64958000000E-01
  3.5111000000      -1.2601700000
  1.6789000000       1.6619080000
 0.76040000000     -0.78750100000
*
h aug-cc-pVTZ-2c
# h     (6s3p2d) / [4s3p2d]     {3111/111/11}
*
   3  s
  33.870000000      0.60680000000E-02
  5.0950000000      0.45308000000E-01
  1.1590000000      0.20282200000
   1  s
 0.32580000000       1.0000000000
   1  s
 0.10270000000       1.0000000000
   1  p
  1.4070000000       1.0000000000
   1  p
 0.38800000000       1.0000000000
   1  d
  1.0570000000       1.0000000000
   1  s
 0.25260000000E-01   1.0000000000
   1  p
 0.10200000000       1.0000000000
   1  d
 0.24700000000       1.0000000000
*
$ecp
*
u def-ecp-2c
*
  ncore =    60           lmax =     5 lsomax =     3
#        coefficient   r^n          exponent
h
           0.0000000    2           1.0000000
s-h
         536.5166278    2          16.4140387
p-h
         169.5449247    2           9.0605561
d-h
         142.6155984    2           8.8318320
f-h
          60.3930760    2           7.0185163
g-h
         -60.1299896    2          12.8040884
*
p
          14.9014290    2           9.0605561
d
           2.7271241    2           8.8318320
f
           0.6545577    2           7.0185163
*
$end

auxbasis:
Code: [Select]
$jbas
*
u def-TZVPP
# u     (18s7p7d6f6g3h5i) / [14s7p7d6f5g2h2i]
# {51111111111111/1111111/1111111/111111/21111/21/41}
*
   5  s
  13742.500811     -0.68213100000E-01
  6430.0766389      0.20700760000
  3021.4532458     -0.34837640000
  1425.4526776      0.46070690000
  675.01494820     -0.55918360000
   1  s
  320.76191510      0.66900730000
   1  s
  152.91319600     -0.90454700000
   1  s
  73.110995400       1.5492018000
   1  s
  35.049170700      -3.7437433000
   1  s
  16.842668900       11.319931900
   1  s
  8.1107708000      -23.456852900
   1  s
  3.9130064000       17.730692700
   1  s
  1.8907526000      0.61974850000
   1  s
 0.91477120000       2.4223749000
   1  s
 0.44301800000      0.78188630000
   1  s
 0.21470320000      0.65872200000E-01
   1  s
 0.10409760000      0.13688050000
   1  s
 0.50478300000E-01  0.55678000000E-02
   1  p
  6.9552087000      0.47220900000E-01
   1  p
  3.5370285000     -0.92623900000E-01
   1  p
  1.6052354000      0.19047900000E-01
   1  p
 0.72901260000     -0.98887000000E-02
   1  p
 0.37149380000     -0.16967700000E-01
   1  p
 0.18466260000      0.36710200000E-01
   1  p
 0.91792300000E-01  0.79083000000E-02
   1  d
  12.418130400     -0.10938100000E-01
   1  d
  6.2504737000      0.24507400000E-01
   1  d
  2.9525926000     -0.17678700000E-01
   1  d
  1.0056114000     -0.95659000000E-02
   1  d
 0.43368970000      0.41860000000E-02
   1  d
 0.19499920000      0.14255200000E-01
   1  d
 0.79037700000E-01  0.28594000000E-02
   1  f
  19.328711200      0.39398000000E-02
   1  f
  7.4341200000     -0.89105000000E-02
   1  f
  2.8592770000      0.23839000000E-02
   1  f
  1.0997220000      0.23839000000E-02
   1  f
 0.19459020000     -0.42039000000E-02
   1  f
 0.74842400000E-01 -0.31930000000E-03
   2  g
  13.415382400     -0.44890000000E-03
  5.9640005000      0.42541000000E-02
   1  g
  3.0338553000     -0.56753000000E-02
   1  g
  1.2962023000     -0.31094000000E-02
   1  g
 0.54826030000      0.37782000000E-02
   1  g
 0.23660820000      0.41990000000E-03
   2  h
  5.7338652000      0.39814000000E-02
  1.0802748000     -0.43263000000E-02
   1  h
 0.29039670000     -0.13615000000E-02
   4  i
  9.3867906000      0.30190000000E-02
  4.2571400000      0.10761600000E-01
  1.8187374000      0.62808000000E-02
 0.73191400000      0.12325000000E-02
   1  i
 0.31270780000      0.79400000000E-04
*
h universal
# h     (5s2p1d) / [3s1p1d]     {311/2/1}
*
   3  s
  15.675292700      0.18688600000E-01
  3.6063578000      0.63167000000E-01
  1.2080016000      0.12046090000
   1  s
 0.47267940000      0.59248500000E-01
   1  s
 0.20181000000      0.51272000000E-02
   2  p
  2.0281365000       1.0000000000
 0.53587300000       1.0000000000
   1  d
  2.2165124000      0.33116000000E-02
*
$end


JakubV


JakubV

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Re: Heavy elements and relativistic effects
« Reply #5 on: April 10, 2023, 03:48:21 AM »
P.S.:

Please, which standard basis did you use?
I tried

u def-TZVPP
h dhf-TZVP-2c
u dhf-ecp-2c

And it is NaNing as well :-(

uwe

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Re: Heavy elements and relativistic effects
« Reply #6 on: April 17, 2023, 06:30:00 PM »
Hi,

using your basis set also leads to 'normal' results in all my tests.

If I use define to prepare the input as usual, and then run the two-component calculation, I do get a different occupation for the spinors:

$spinor shells
 a       1-33                                   ( 1 )

And in your input:

$spinor shells
 a       1-14                                   ( 2 )
 a       19-20                                  ( 1 )

Did you modify the occupation by hand? To my understanding each spinor should be the place for one electron only. For UH this would be 92 (U) + 1 (H) - 60 (ECP) = 33 electrons (60 electrons are put in the ECP).

If you do not add $kramers to the control file, the 2c job is unrestricted (similar to UHF), if you add $kramers you enable a Kramers-restricted scheme (similar to RHF). Well, for 33 electrons $kramers does not make sense, obviously...


JakubV

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Re: Heavy elements and relativistic effects
« Reply #7 on: April 19, 2023, 12:14:43 AM »
Hello,

Thank you. I forgot to manually add $kramers into the control file.
No, I did not edit the occupations by hand.

I posted the control file *after the run*. It somehow even cut electrons out, as 1-14 occupied twice gives 28, and 19-20 gives two additional electrons, thus 30.

I was running define and gave molecular charge "1" as I am interested in closed-shell species UH+ now. So my control *before the run* was

Code: [Select]
$title
$symmetry c1
$user-defined bonds    file=coord
$coord    file=coord
$optimize
 internal   off
 redundant  off
 cartesian  on
 global     off
 basis      off
$atoms
u  1                                                                           \
   basis =u Cao-2c                                                             \
   ecp   =u def-ecp-2c                                                         \
   jbas  =u def-TZVPP
h  2                                                                           \
   basis =h aug-cc-pVTZ-2c                                                     \
   jbas  =h universal
$basis    file=basis
$ecp    file=basis
$scfmo   file=mos
$closed shells
 a       1-14                                   ( 2 )
$open shells type=1
 a       15-18                                  ( 1 )
$roothaan         1
      a = 6/7      b = 6/7
$scfiterlimit     8000
$scfconv        8
$thize     0.10000000E-04
$thime        5
$scfdamp   start=2.000  step=0.050  min=0.50
$scfdump
$scfintunit
 unit=30       size=0        file=twoint
$scfdiis
$maxcor    500 MiB  per_core
$scforbitalshift  closedshell=.4
$drvopt
   cartesian  on
   basis      off
   global     off
   hessian    on
   dipole     on
   nuclear polarizability
$interconversion  off
   qconv=1.d-7
   maxiter=25
$coordinateupdate
   dqmax=0.3
   interpolate  on
   statistics    5
$forceupdate
   ahlrichs numgeo=0  mingeo=3 maxgeo=4 modus=<g|dq> dynamic fail=0.3
   threig=0.005  reseig=0.005  thrbig=3.0  scale=1.00  damping=0.0
$forceinit on
   diag=default
$energy    file=energy
$grad    file=gradient
$forceapprox    file=forceapprox
$soghf
$ricore      800
$rij
$jbas    file=auxbasis
$rundimensions
   natoms=2
   nbf(CAO)=164
   nbf(AO)=127
$last step     define
$end

Here 1-14 twice (28e) + 4 unpaired electrons in 15-18 gives 32 electrons of UH+ with 60e ECP-2c on uranium.

Best regards,
Jakub

JakubV

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Re: Heavy elements and relativistic effects
« Reply #8 on: April 19, 2023, 01:22:22 AM »
P.S.:  I tried to add $kramers and it is still NaNing...

As for my special basis/ecp - directory "Kramers"
As for the standard basis: "Kramers_Standard"

Directories contain inputs, outputs are in "output".


uwe

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Re: Heavy elements and relativistic effects
« Reply #9 on: April 20, 2023, 10:33:25 AM »
Hello,

thanks for the input data, ROHF does indeed not work as an input for two-component calculations. So either RHF or UHF can serve as starting point, not ROHF.

ridft should stop in such cases to avoid getting weird results (although sometimes it can be very interesting to combine things that were not meant to be combined to go in a new direction, but probably not in this case...)

Best Regards, Uwe