Hello!
I was recently running an Na+ and water dimer calculation at the PBE0/aug-cc-pVTZ level with the Na+ as a ghost atom. The SCF procedure (DF-RKS) does not converge in 100 iterations. Strangely, when the Na+ and water dimer is close (equilibrium distance) the SCF converges, but as I increase the distance between Na+ and water, the SCF stops converging. I was wondering if anyone could help with this issue. I’ve attached the input and output files below. Thank you!
Input and output:
basis {
assign aug-cc-pvtz
}
molecule H2O {
no_reorient
no_com
units bohr
0 1
O 0.00000000 0.00000000 0.00000000
H -1.11259885 1.43458170 0.00000000
H -1.11259885 -1.43458170 0.00000000
@Na 8.38998655 0.00000000 0.00000000
}
set {
ints_tolerance 1.0E-10
s_tolerance 1.0E-07
dft_grac_shift 0.129493
}
energy, wfn = energy('PBE0', return_wfn=True)
fchk_writer = psi4.FCHKWriter(wfn)
fchk_writer.write('NaH2O_A.fchk')
-----------------------------------------------------------------------
Psi4: An Open-Source Ab Initio Electronic Structure Package
Psi4 1.4a1 prerelease
Git: Rev {} 9c877d0
D. G. A. Smith, L. A. Burns, A. C. Simmonett, R. M. Parrish,
M. C. Schieber, R. Galvelis, P. Kraus, H. Kruse, R. Di Remigio,
A. Alenaizan, A. M. James, S. Lehtola, J. P. Misiewicz, M. Scheurer,
R. A. Shaw, J. B. Schriber, Y. Xie, Z. L. Glick, D. A. Sirianni,
J. S. O'Brien, J. M. Waldrop, A. Kumar, E. G. Hohenstein,
B. P. Pritchard, B. R. Brooks, H. F. Schaefer III, A. Yu. Sokolov,
K. Patkowski, A. E. DePrince III, U. Bozkaya, R. A. King,
F. A. Evangelista, J. M. Turney, T. D. Crawford, C. D. Sherrill,
J. Chem. Phys. 152(18) 184108 (2020). https://doi.org/10.1063/5.0006002
Additional Code Authors
E. T. Seidl, C. L. Janssen, E. F. Valeev, M. L. Leininger,
J. F. Gonthier, R. M. Richard, H. R. McAlexander, M. Saitow, X. Wang,
P. Verma, and M. H. Lechner
Previous Authors, Complete List of Code Contributors,
and Citations for Specific Modules
https://github.com/psi4/psi4/blob/master/codemeta.json
https://github.com/psi4/psi4/graphs/contributors
http://psicode.org/psi4manual/master/introduction.html#citing-psifour
-----------------------------------------------------------------------
Psi4 started on: Sunday, 26 December 2021 07:29PM
Process ID: 305680
Host: moses-razer
PSIDATADIR: /usr/local/psi4/share/psi4
Memory: 500.0 MiB
Threads: 1
==> Input File <==
--------------------------------------------------------------------------
memory 8 GB
basis {
assign aug-cc-pvtz
}
molecule H2O {
no_reorient
no_com
units bohr
0 1
O 0.00000000 0.00000000 0.00000000
H -1.11259885 1.43458170 0.00000000
H -1.11259885 -1.43458170 0.00000000
@Na 8.38998655 0.00000000 0.00000000
}
set {
ints_tolerance 1.0E-10
s_tolerance 1.0E-07
dft_grac_shift 0.129493
}
energy, wfn = energy('PBE0', return_wfn=True)
fchk_writer = psi4.FCHKWriter(wfn)
fchk_writer.write('NaH2O_A.fchk')
--------------------------------------------------------------------------
Memory set to 7.451 GiB by Python driver.
Scratch directory: /scratch/
*** tstart() called on moses-razer
*** at Sun Dec 26 19:29:06 2021
=> Loading Basis Set <=
Name: ANONYMOUS5312A9A5
Role: ORBITAL
Keyword: BASIS
atoms 1 entry O line 331 file /home/kchung25/anaconda3/envs/p4env/share/psi4/basis/aug-cc-pvtz.gbs
atoms 2-3 entry H line 40 file /home/kchung25/anaconda3/envs/p4env/share/psi4/basis/aug-cc-pvtz.gbs
atoms 4 entry NA line 469 file /home/kchung25/anaconda3/envs/p4env/share/psi4/basis/aug-cc-pvtz.gbs
---------------------------------------------------------
SCF
by Justin Turney, Rob Parrish, Andy Simmonett
and Daniel G. A. Smith
RKS Reference
1 Threads, 7629 MiB Core
---------------------------------------------------------
==> Geometry <==
Molecular point group: c2v
Full point group: C2v
Geometry (in Bohr), charge = 0, multiplicity = 1:
Center X Y Z Mass
------------ ----------------- ----------------- ----------------- -----------------
O 0.000000000000 0.000000000000 0.000000000000 15.994914619570
H -1.112598850000 1.434581700000 0.000000000000 1.007825032230
H -1.112598850000 -1.434581700000 0.000000000000 1.007825032230
Gh(NA) 8.389986550000 0.000000000000 0.000000000000 22.989769282000
Running in c2v symmetry.
Rotational constants: A = 14.51204 B = 0.03714 C = 0.03705 [cm^-1]
Rotational constants: A = 435060.06858 B = 1113.49610 C = 1110.65349 [MHz]
Nuclear repulsion = 9.161719190563474
Charge = 0
Multiplicity = 1
Electrons = 10
Nalpha = 5
Nbeta = 5
==> Algorithm <==
SCF Algorithm Type is DF.
DIIS enabled.
MOM disabled.
Fractional occupation disabled.
Guess Type is SAD.
Energy threshold = 1.00e-06
Density threshold = 1.00e-06
Integral threshold = 1.00e-10
==> Primary Basis <==
Basis Set: ANONYMOUS5312A9A5
Blend: AUG-CC-PVTZ
Number of shells: 48
Number of basis function: 142
Number of Cartesian functions: 164
Spherical Harmonics?: true
Max angular momentum: 3
==> DFT Potential <==
=> Composite Functional: PBE0 <=
PBE0 Hyb-GGA Exchange-Correlation Functional
C. Adamo and V. Barone, J. Chem. Phys. 110, 6158 (1999)
M. Ernzerhof and G. E. Scuseria, J. Chem. Phys. 110, 5029 (1999)
Deriv = 1
GGA = TRUE
Meta = FALSE
Exchange Hybrid = TRUE
MP2 Hybrid = FALSE
=> Exchange Functionals <=
0.7500 Perdew, Burke & Ernzerhof
=> Exact (HF) Exchange <=
0.2500 HF
=> Correlation Functionals <=
1.0000 Perdew, Burke & Ernzerhof
=> Asymptotic Correction <=
X Functional = XC_GGA_X_LB
C Functional = XC_LDA_C_VWN
Bulk Shift = 0.129493
GRAC Alpha = 0.500000
GRAC Beta = 40.000000
=> Molecular Quadrature <=
Radial Scheme = TREUTLER
Pruning Scheme = NONE
Nuclear Scheme = TREUTLER
BS radius alpha = 1
Pruning alpha = 1
Radial Points = 75
Spherical Points = 302
Total Points = 89025
Total Blocks = 768
Max Points = 256
Max Functions = 142
Weights Tolerance = 1.00E-15
=> Loading Basis Set <=
Name: (ANONYMOUS5312A9A5 AUX)
Role: JKFIT
Keyword: DF_BASIS_SCF
atoms 1 entry O line 286 file /home/kchung25/anaconda3/envs/p4env/share/psi4/basis/aug-cc-pvtz-jkfit.gbs
atoms 2-3 entry H line 70 file /home/kchung25/anaconda3/envs/p4env/share/psi4/basis/aug-cc-pvtz-jkfit.gbs
atoms 4 entry NA line 498 file /home/kchung25/anaconda3/envs/p4env/share/psi4/basis/def2-universal-jkfit.gbs
==> Integral Setup <==
DFHelper Memory: AOs need 0.051 GiB; user supplied 5.260 GiB. Using in-core AOs.
==> MemDFJK: Density-Fitted J/K Matrices <==
J tasked: Yes
K tasked: Yes
wK tasked: No
OpenMP threads: 1
Memory [MiB]: 5385
Algorithm: Core
Schwarz Cutoff: 1E-10
Mask sparsity (%): 0.2777
Fitting Condition: 1E-10
=> Auxiliary Basis Set <=
Basis Set: (ANONYMOUS5312A9A5 AUX)
Blend: AUG-CC-PVTZ-JKFIT + DEF2-UNIVERSAL-JKFIT
Number of shells: 92
Number of basis function: 308
Number of Cartesian functions: 378
Spherical Harmonics?: true
Max angular momentum: 4
Cached 100.0% of DFT collocation blocks in 0.328 [GiB].
Minimum eigenvalue in the overlap matrix is 2.8509124349E-04.
Reciprocal condition number of the overlap matrix is 4.4202777885E-05.
Using symmetric orthogonalization.
==> Pre-Iterations <==
SCF Guess: Superposition of Atomic Densities via on-the-fly atomic UHF (no occupation information).
-------------------------
Irrep Nso Nmo
-------------------------
A1 56 56
A2 17 17
B1 39 39
B2 30 30
-------------------------
Total 142 142
-------------------------
==> Iterations <==
Total Energy Delta E RMS |[F,P]|
@DF-RKS iter SAD: -75.97620479579365 -7.59762e+01 0.00000e+00
@DF-RKS iter 1: 5.65092262388474 8.16271e+01 1.83142e-02 DIIS
@DF-RKS iter 2: -60.84054872545652 -6.64915e+01 1.08135e-01 DIIS
@DF-RKS iter 3: -61.47994738951796 -6.39399e-01 1.06037e-01 DIIS
@DF-RKS iter 4: -61.94478351763251 -4.64836e-01 1.04519e-01 DIIS
@DF-RKS iter 5: -61.97521287500297 -3.04294e-02 1.04418e-01 DIIS
@DF-RKS iter 6: -61.98703003724567 -1.18172e-02 1.04378e-01 DIIS
@DF-RKS iter 7: -61.99633324938624 -9.30321e-03 1.04347e-01 DIIS
@DF-RKS iter 8: -61.99543762580062 8.95624e-04 1.04350e-01 DIIS
@DF-RKS iter 9: -61.99525354217147 1.84084e-04 1.04351e-01 DIIS
@DF-RKS iter 10: -61.99593808905948 -6.84547e-04 1.04349e-01 DIIS
@DF-RKS iter 11: -62.03283023560814 -3.68921e-02 1.04225e-01 DIIS
@DF-RKS iter 12: -62.05885038138891 -2.60201e-02 1.04143e-01 DIIS
@DF-RKS iter 13: -62.02453113237811 3.43192e-02 1.04257e-01 DIIS
@DF-RKS iter 14: -62.02447199478910 5.91376e-05 1.04256e-01 DIIS
@DF-RKS iter 15: -62.06180209135522 -3.73301e-02 1.04132e-01 DIIS
@DF-RKS iter 16: -62.05736617460333 4.43592e-03 1.04146e-01 DIIS
@DF-RKS iter 17: -62.05852107407755 -1.15490e-03 1.04143e-01 DIIS
@DF-RKS iter 18: -62.09450975212263 -3.59887e-02 1.04033e-01 DIIS
@DF-RKS iter 19: -62.11702903435923 -2.25193e-02 1.03946e-01 DIIS
@DF-RKS iter 20: -62.10729098497010 9.73805e-03 1.03977e-01 DIIS
@DF-RKS iter 21: -62.08902790451533 1.82631e-02 1.04041e-01 DIIS
@DF-RKS iter 22: -62.09714953945048 -8.12163e-03 1.04011e-01 DIIS
@DF-RKS iter 23: -62.08684720506605 1.03023e-02 1.04049e-01 DIIS
@DF-RKS iter 24: -62.08533808190586 1.50912e-03 1.04053e-01 DIIS
@DF-RKS iter 25: -62.09396388652315 -8.62580e-03 1.04023e-01 DIIS
@DF-RKS iter 26: -62.09138586222104 2.57802e-03 1.04030e-01 DIIS
@DF-RKS iter 27: -62.06532692096742 2.60589e-02 1.04111e-01 DIIS
@DF-RKS iter 28: -62.06765039747845 -2.32348e-03 1.04117e-01 DIIS
@DF-RKS iter 29: -62.05462543989105 1.30250e-02 1.04146e-01 DIIS
@DF-RKS iter 30: -62.07503072642499 -2.04053e-02 1.04093e-01 DIIS
@DF-RKS iter 31: -62.05027070606336 2.47600e-02 1.04161e-01 DIIS
@DF-RKS iter 32: -62.08215463114397 -3.18839e-02 1.04069e-01 DIIS
@DF-RKS iter 33: -62.04576881242298 3.63858e-02 1.04177e-01 DIIS
@DF-RKS iter 34: -62.09191422102469 -4.61454e-02 1.04037e-01 DIIS
@DF-RKS iter 35: -62.04301968852170 4.88945e-02 1.04189e-01 DIIS
@DF-RKS iter 36: -62.07132228787025 -2.83026e-02 1.04098e-01 DIIS
@DF-RKS iter 37: -62.05716477401588 1.41575e-02 1.04144e-01 DIIS
@DF-RKS iter 38: -62.06796922682510 -1.08045e-02 1.04109e-01 DIIS
@DF-RKS iter 39: -62.06251062611473 5.45860e-03 1.04126e-01 DIIS
@DF-RKS iter 40: -62.06551246327705 -3.00184e-03 1.04117e-01 DIIS
@DF-RKS iter 41: -62.06437648564841 1.13598e-03 1.04120e-01 DIIS
@DF-RKS iter 42: -62.06454814189595 -1.71656e-04 1.04120e-01 DIIS
@DF-RKS iter 43: -62.06488577567828 -3.37634e-04 1.04119e-01 DIIS
@DF-RKS iter 44: -62.06436316533912 5.22610e-04 1.04120e-01 DIIS
@DF-RKS iter 45: -62.06490507882803 -5.41913e-04 1.04119e-01 DIIS
@DF-RKS iter 46: -62.06441309857446 4.91980e-04 1.04120e-01 DIIS
@DF-RKS iter 47: -62.06483266050017 -4.19562e-04 1.04119e-01 DIIS
@DF-RKS iter 48: -62.06448280576963 3.49855e-04 1.04120e-01 DIIS
@DF-RKS iter 49: -62.06477662749186 -2.93822e-04 1.04119e-01 DIIS
@DF-RKS iter 50: -62.06452416964802 2.52458e-04 1.04120e-01 DIIS
@DF-RKS iter 51: -62.06474869203950 -2.24522e-04 1.04119e-01 DIIS
@DF-RKS iter 52: -62.06454235243921 2.06340e-04 1.04120e-01 DIIS
@DF-RKS iter 53: -62.06473740746520 -1.95055e-04 1.04119e-01 DIIS
@DF-RKS iter 54: -62.06454951758124 1.87890e-04 1.04120e-01 DIIS
@DF-RKS iter 55: -62.06473266657411 -1.83149e-04 1.04119e-01 DIIS
@DF-RKS iter 56: -62.06455313651009 1.79530e-04 1.04120e-01 DIIS
@DF-RKS iter 57: -62.06472958729570 -1.76451e-04 1.04119e-01 DIIS
@DF-RKS iter 58: -62.06455615558124 1.73432e-04 1.04120e-01 DIIS
@DF-RKS iter 59: -62.06472656882020 -1.70413e-04 1.04119e-01 DIIS
@DF-RKS iter 60: -62.06455931008779 1.67259e-04 1.04120e-01 DIIS
@DF-RKS iter 61: -62.06472333789061 -1.64028e-04 1.04119e-01 DIIS
@DF-RKS iter 62: -62.06456261939551 1.60718e-04 1.04120e-01 DIIS
@DF-RKS iter 63: -62.06472013193836 -1.57513e-04 1.04119e-01 DIIS
@DF-RKS iter 64: -62.06456579055730 1.54341e-04 1.04120e-01 DIIS
@DF-RKS iter 65: -62.06471706544318 -1.51275e-04 1.04119e-01 DIIS
@DF-RKS iter 66: -62.06456885725034 1.48208e-04 1.04120e-01 DIIS
@DF-RKS iter 67: -62.06471408208424 -1.45225e-04 1.04119e-01 DIIS
@DF-RKS iter 68: -62.06457180998545 1.42272e-04 1.04120e-01 DIIS
@DF-RKS iter 69: -62.06471124475806 -1.39435e-04 1.04119e-01 DIIS
@DF-RKS iter 70: -62.06457461133655 1.36633e-04 1.04120e-01 DIIS
@DF-RKS iter 71: -62.06470855749651 -1.33946e-04 1.04119e-01 DIIS
@DF-RKS iter 72: -62.06457727060224 1.31287e-04 1.04120e-01 DIIS
@DF-RKS iter 73: -62.06470596957332 -1.28699e-04 1.04119e-01 DIIS
@DF-RKS iter 74: -62.06457980730441 1.26162e-04 1.04120e-01 DIIS
@DF-RKS iter 75: -62.06470355228291 -1.23745e-04 1.04119e-01 DIIS
@DF-RKS iter 76: -62.06458220013032 1.21352e-04 1.04120e-01 DIIS
@DF-RKS iter 77: -62.06470120723195 -1.19007e-04 1.04119e-01 DIIS
@DF-RKS iter 78: -62.06458456723347 1.16640e-04 1.04120e-01 DIIS
@DF-RKS iter 79: -62.06469891366358 -1.14346e-04 1.04119e-01 DIIS
@DF-RKS iter 80: -62.06458683087752 1.12083e-04 1.04120e-01 DIIS
@DF-RKS iter 81: -62.06469672580488 -1.09895e-04 1.04119e-01 DIIS
@DF-RKS iter 82: -62.06458898098231 1.07745e-04 1.04120e-01 DIIS
@DF-RKS iter 83: -62.06469461362907 -1.05633e-04 1.04119e-01 DIIS
@DF-RKS iter 84: -62.06459110898181 1.03505e-04 1.04120e-01 DIIS
@DF-RKS iter 85: -62.06469257654425 -1.01468e-04 1.04119e-01 DIIS
@DF-RKS iter 86: -62.06459308923888 9.94873e-05 1.04120e-01 DIIS
@DF-RKS iter 87: -62.06469064600990 -9.75568e-05 1.04119e-01 DIIS
@DF-RKS iter 88: -62.06459501718618 9.56288e-05 1.04120e-01 DIIS
@DF-RKS iter 89: -62.06468874907403 -9.37319e-05 1.04119e-01 DIIS
@DF-RKS iter 90: -62.06459691688129 9.18322e-05 1.04120e-01 DIIS
@DF-RKS iter 91: -62.06468688852454 -8.99716e-05 1.04119e-01 DIIS
@DF-RKS iter 92: -62.06459873474731 8.81538e-05 1.04120e-01 DIIS
@DF-RKS iter 93: -62.06468541070467 -8.66760e-05 1.04119e-01 DIIS
@DF-RKS iter 94: -62.06458853417276 9.68765e-05 1.04120e-01 DIIS
@DF-RKS iter 95: -62.06468744654792 -9.89124e-05 1.04119e-01 DIIS
@DF-RKS iter 96: -62.06459876155064 8.86850e-05 1.04120e-01 DIIS
@DF-RKS iter 97: -62.06468345066283 -8.46891e-05 1.04119e-01 DIIS
@DF-RKS iter 98: -62.06459136377997 9.20869e-05 1.04120e-01 DIIS
@DF-RKS iter 99: -62.06468415490521 -9.27911e-05 1.04119e-01 DIIS
@DF-RKS iter 100: -62.06460224860098 8.19063e-05 1.04120e-01 DIIS
PsiException: Could not converge SCF iterations in 100 iterations.
Failed to converge.
Traceback (most recent call last):
File "/usr/local/psi4/bin/psi4", line 337, in <module>
exec(content)
File "<string>", line 45, in <module>
File "/usr/local/psi4/lib/psi4/driver/driver.py", line 576, in energy
wfn = procedures['energy'][lowername](lowername, molecule=molecule, **kwargs)
File "/usr/local/psi4/lib/psi4/driver/procrouting/proc.py", line 2238, in run_scf
scf_wfn = scf_helper(name, post_scf=False, **kwargs)
File "/usr/local/psi4/lib/psi4/driver/procrouting/proc.py", line 1528, in scf_helper
e_scf = scf_wfn.compute_energy()
File "/usr/local/psi4/lib/psi4/driver/procrouting/scf_proc/scf_iterator.py", line 93, in scf_compute_energy
raise e
File "/usr/local/psi4/lib/psi4/driver/procrouting/scf_proc/scf_iterator.py", line 86, in scf_compute_energy
self.iterations()
File "/usr/local/psi4/lib/psi4/driver/procrouting/scf_proc/scf_iterator.py", line 464, in scf_iterate
raise SCFConvergenceError("""SCF iterations""", self.iteration_, self, Ediff, Dnorm)
psi4.driver.p4util.exceptions.SCFConvergenceError: Could not converge SCF iterations in 100 iterations.
Printing out the relevant lines from the Psithon --> Python processed input file:
""","H2O")
core.IO.set_default_namespace("H2O")
core.set_global_option("INTS_TOLERANCE", 1.0E-10)
core.set_global_option("S_TOLERANCE", 1.0E-07)
core.set_global_option("DFT_GRAC_SHIFT", 0.129493)
--> energy, wfn = energy('PBE0', return_wfn=True)
fchk_writer = psi4.core.FCHKWriter(wfn)
fchk_writer.write('NaH2O_A.fchk')
!-------------------------------------------------------!
! !
! Could not converge SCF iterations in 100 iterations. !
! !
!-------------------------------------------------------!
Psi4 stopped on: Sunday, 26 December 2021 07:30PM
Psi4 wall time for execution: 0:01:04.79
*** Psi4 encountered an error. Buy a developer more coffee!
*** Resources and help at github.com/psi4/psi4.