Dunning's aug-cc basis set convergence


Just Got Here
Greetings,

I have been trying to converge a LiOH calculation using an aug-cc-PV5Z projected from a cc-pV5Z basis set. I have no problems with the first SCF using cc-pV5Z, nevertheless with the aug-cc-pV5Z after the second SCF cycle I get an energy considerably different from the previous one and keeps going like it. Disabling DIIS, changing damping, lshift or projecting from a HF calculation does not help either. Does anyone know how this inconvenient may be solved? I would appreciate any ideas or help. By the way, I am using version 6.6

Here is the input:

title "LiOH charge 0"
echo
memory total 3 Gb

basis small; * library cc-pV5Z ; end
basis large; * library aug-cc-pV5Z ; end

charge 0
set lindep:tol 1d-10
set int:acc_std 1d-14

geometry noautosym noautoz
 Li           0.0000000000        0.0000000000        0.0000000000
O 0.0000000000 0.0000000000 2.9895465126
H 0.0000037795 0.0000000000 4.8206909947
end

set "ao basis" small
dft
 vectors input atomic output small.mos
xc becke86b
mult 1
direct ; decomp ; maxiter 300
convergence lshift 0.3
end
task dft

set "ao basis" large
dft
 vectors input project small small.mos output large.mos
xc becke86b
mult 1
convergence energy 1e-7
direct ; decomp ; maxiter 300
convergence nodiis damp 30 ncydp 300 lshift 0.5
tolerances tight
end

task dft energy

Here is the second part of the output with the aug-cc-pV5Z basis set, I cut the rest of the SCF because it remains practically the same.

           General Information
-------------------
SCF calculation type: DFT
Wavefunction type: closed shell.
No. of atoms  : 3
No. of electrons : 12
Alpha electrons : 6
Beta electrons : 6
Charge  : 0
Spin multiplicity: 1
Use of symmetry is: off; symmetry adaption is: off
Maximum number of iterations: 300
This is a Direct SCF calculation.
AO basis - number of functions: 469
number of shells: 74
Convergence on energy requested: 1.00D-07
Convergence on density requested: 1.00D-05
Convergence on gradient requested: 5.00D-04

             XC Information
--------------
Becke 1986 Exchange Functional 1.000

            Grid Information
----------------
Grid used for XC integration: medium
Radial quadrature: Mura-Knowles
Angular quadrature: Lebedev.
Tag B.-S. Rad. Rad. Pts. Rad. Cut. Ang. Pts.
--- ---------- --------- --------- ---------
Li 1.45 49 20.0 434
O 0.60 49 16.0 434
H 0.35 45 23.0 434
Grid pruning is: on
Number of quadrature shells: 143
Spatial weights used: Erf1

         Convergence Information
-----------------------
Convergence aids based upon iterative change in
total energy or number of iterations.
Levelshifting, if invoked, occurs when the
HOMO/LUMO gap drops below (HL_TOL): 1.00D-02
DIIS, if invoked, will attempt to extrapolate
using up to (NFOCK): 10 stored Fock matrices.

                   Damping(30%)  Levelshifting(0.5)       DIIS
--------------- ------------------- ---------------
dE on: start ASAP start
dE off: 300 iters 300 iters 300 iters


     Screening Tolerance Information
-------------------------------
Density screening/tol_rho: 1.00D-10
AO Gaussian exp screening on grid/accAOfunc: 16
CD Gaussian exp screening on grid/accCDfunc: 20
XC Gaussian exp screening on grid/accXCfunc: 20
Schwarz screening/accCoul: 1.00D-08


Setting tolerance for linear dependence to 1.00D-10

   Orbital projection guess
------------------------

Filename           = ./small.mos
Old title = "LiOH charge 0"
Old basis size = 322
Old no. of sets = 1
Old no. of MOs = 322
Old basis name = small
Basis name on file = small


int_init: setting std/high accuracies to 1.0D-14 1.0D-28

int_init: setting std/high accuracies to 1.0D-14 1.0D-28
  Time after variat. SCF:   3910.9
Time prior to 1st pass: 3910.9

Grid_pts file          = ./nwchem.gridpts.0
Record size in doubles = 12289 No. of grid_pts per rec = 3070
Max. records in memory = 24 Max. recs in file = 4227728


          Memory utilization after 1st SCF pass:
Heap Space remaining (MW): 100.36 100358070
Stack Space remaining (MW): 100.66 100661044

  convergence    iter        energy       DeltaE   RMS-Dens  Diis-err    time
---------------- ----- ----------------- --------- --------- --------- ------
d=30,ls=0.5,diis 1 -82.8019578490 -8.97D+01 1.61D+06 7.01D-02 4388.0
Grid integrated density: 12.000374854549
Requested integration accuracy: 0.10E-05
Singularity in Pulay matrix. Error and Fock matrices removed.
d=30,ls=0.5,diis 2****************** -1.14D+11 1.83D+05 2.34D+22 4922.1

Forum Vet
I repeat the calculation for two times bu your input provided here, and get the error
...
bas_tag_lib: failed to locate basis li_aug-cc-pv5z in file /.../src/basis/libraries/
------------------------------------------------------------------------
bas_tag_lib: no such basis available 0
------------------------------------------------------------------------
------------------------------------------------------------------------
current input line :
54: task dft energy
------------------------------------------------------------------------
------------------------------------------------------------------------
bas_tag_lib: failed to locate basis li_aug-cc-pv5z in file /.../src/basis/libraries/
bas_tag_lib: no such basis available 0
------------------------------------------------------------------------
------------------------------------------------------------------------
current input line :
0:
------------------------------------------------------------------------
------------------------------------------------------------------------
There is an error in the input file
bas_tag_lib: failed to locate basis li_aug-cc-pv5z in file /.../src/basis/libraries/
bas_tag_lib: no such basis available 0
------------------------------------------------------------------------
------------------------------------------------------------------------
which means the basis set is not available for Li.

Forum Vet
I repeat the calculation for two times bu your input provided here using NWCHEM6.8, and get the same error
...
d= 0,ls=0.3,diis 29 -82.8019645120 -6.09D-07 9.92D-06 7.68D-07 585.8

Total DFT energy = -82.801964959130
...
Multipole analysis of the density
---------------------------------

...
    2   0 0 2     10.678693    -40.941532    -40.941532     92.561757


Task  times  cpu:      615.4s     wall:      615.4s


                               NWChem Input Module
-------------------



                                NWChem DFT Module
-----------------


                                  LiOH charge 0


bas_tag_lib: failed to locate basis li_aug-cc-pv5z in file /.../src/basis/libraries/
------------------------------------------------------------------------
bas_tag_lib: no such basis available 0
------------------------------------------------------------------------
------------------------------------------------------------------------
current input line :
54: task dft energy
------------------------------------------------------------------------
------------------------------------------------------------------------
bas_tag_lib: failed to locate basis li_aug-cc-pv5z in file /.../src/basis/libraries/
bas_tag_lib: no such basis available 0
------------------------------------------------------------------------
------------------------------------------------------------------------
current input line :
0:
------------------------------------------------------------------------
------------------------------------------------------------------------
There is an error in the input file
bas_tag_lib: failed to locate basis li_aug-cc-pv5z in file /.../src/basis/libraries/
bas_tag_lib: no such basis available 0
------------------------------------------------------------------------
------------------------------------------------------------------------
which means the basis set requested is not available for Li.

Just Got Here
I certainly did not include the basis set for Li, sorry my bad. Here it is:

basis "Li_aug-cc-pV5Z" SPHERICAL
Li S
29493.0000000    0.000020099982   -0.000015637377
4417.1010000 0.000157449858 -0.000114674095
1005.2230000 0.000825215924 -0.000599432770
284.7009000 0.003469480212 -0.002538467469
92.8654300 0.012434072146 -0.009100953183
33.5117900 0.038714798501 -0.028772772950
13.0418000 0.102924190732 -0.077811585979
5.3575360 0.222859666159 -0.178297368033
2.2793380 0.367199869628 -0.323980380929
0.9939900 0.386338402409 -0.499885230341
Li S
    0.4334710    1.000000000000
Li S
    0.0955660    1.000000000000
Li S
    0.0446570    1.000000000000
Li S
    0.0206330    1.000000000000
Li S
    0.0061000    1.000000000000
Li P
   11.2500000    0.029517231676
2.5000000 0.223134072987
0.6500000 0.844615786255
Li P
    0.2500000    1.000000000000
Li P
    0.1000000    1.000000000000
Li P
    0.0390000    1.000000000000
Li P
    0.0170000    1.000000000000
Li P
    0.0065000    1.000000000000
Li D
    0.5310000    1.000000000000
Li D
    0.2481000    1.000000000000
Li D
    0.1159000    1.000000000000
Li D
    0.0542000    1.000000000000
Li D
    0.0235000    1.000000000000
Li F
    0.2920000    1.000000000000
Li F
    0.1641000    1.000000000000
Li F
    0.0922000    1.000000000000
Li F
    0.0448000    1.000000000000
Li G
    0.2971000    1.000000000000
Li G
    0.1500000    1.000000000000
Li G
    0.0724000    1.000000000000
Li H
    0.2949000    1.000000000000
Li H
    0.0127400    1.000000000000
end

Forum Vet
The following input works
set "ao basis" large
dft
 vectors input atomic output large.mos
 xc becke88 lyp
 mult 1
 convergence energy 1e-7
 direct ; decomp ; maxiter 300
 tolerances tight
end
set quickguess t

task dft energy


Just Got Here


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