I’m having trouble converging DFT calculations for some simple molecules. E.g. CO2 with the data file below gives the output also below, where the energy oscillates wildly from the start. The same system converges easily with NWChem. This is with a recent version of Psi4 (22 May), after a problem with libderiv.h was fixed following a previous post to this forum. Is there a bug, or am I doing something wrong?
memory 8 GB
# Molecule A
molecule {
no_reorient
no_com
units bohr
O1 0.00000000 0.00000000 2.19605057
C 0.00000000 0.00000000 0.00000000
O2 0.00000000 0.00000000 -2.19605057
}
set {
basis aug-cc-pVTZ
reference rhf
ints_tolerance 1.0E-08
s_tolerance 1.0E-08
energy, wfn = energy(‘PBE0’, return_wfn=True)
}
This leads to the following output (truncated):
-----------------------------------------------------------------------
Psi4: An Open-Source Ab Initio Electronic Structure Package
Psi4 1.3rc3.dev29
Git: Rev {master} 766b7e2
R. M. Parrish, L. A. Burns, D. G. A. Smith, A. C. Simmonett,
A. E. DePrince III, E. G. Hohenstein, U. Bozkaya, A. Yu. Sokolov,
R. Di Remigio, R. M. Richard, J. F. Gonthier, A. M. James,
H. R. McAlexander, A. Kumar, M. Saitow, X. Wang, B. P. Pritchard,
P. Verma, H. F. Schaefer III, K. Patkowski, R. A. King, E. F. Valeev,
F. A. Evangelista, J. M. Turney, T. D. Crawford, and C. D. Sherrill,
J. Chem. Theory Comput. 13(7) pp 3185--3197 (2017).
(doi: 10.1021/acs.jctc.7b00174)
Additional Contributions by
P. Kraus, H. Kruse, M. H. Lechner, M. C. Schieber, R. A. Shaw,
A. Alenaizan, R. Galvelis, Z. L. Glick, S. Lehtola, and J. P. Misiewicz
-----------------------------------------------------------------------
Psi4 started on: Monday, 27 May 2019 03:15PM
Process ID: 12476
Host: whirligig
PSIDATADIR: /usr/local/psi4/share/psi4
Memory: 500.0 MiB
Threads: 6
==> Input File <==
--------------------------------------------------------------------------
memory 8 GB
# Molecule A
molecule {
no_reorient
no_com
units bohr
O1 0.00000000 0.00000000 2.19605057
C 0.00000000 0.00000000 0.00000000
O2 0.00000000 0.00000000 -2.19605057
}
set {
basis aug-cc-pVTZ
reference rhf
ints_tolerance 1.0E-08
s_tolerance 1.0E-08
}
energy, wfn = energy('PBE0', return_wfn=True)
fchk_writer = psi4.FCHKWriter(wfn)
fchk_writer.write('CO2_A.fchk')
--------------------------------------------------------------------------
Memory set to 7.451 GiB by Python driver.
*** tstart() called on whirligig
*** at Mon May 27 15:15:54 2019
=> Loading Basis Set <=
Name: AUG-CC-PVTZ
Role: ORBITAL
Keyword: BASIS
atoms 1, 3 entry O line 344 file /home/ajs1/CamCASP/basis/psi4/aug-cc-pvtz.gbs
atoms 2 entry C line 232 file /home/ajs1/CamCASP/basis/psi4/aug-cc-pvtz.gbs
---------------------------------------------------------
SCF
by Justin Turney, Rob Parrish, Andy Simmonett
and Daniel G. A. Smith
RKS Reference
6 Threads, 7629 MiB Core
---------------------------------------------------------
==> Geometry <==
Molecular point group: d2h
Full point group: D_inf_h
Geometry (in Bohr), charge = 0, multiplicity = 1:
Center X Y Z Mass
------------ ----------------- ----------------- ----------------- -----------------
O 0.000000000000 0.000000000000 2.196050570000 15.994914619570
C 0.000000000000 0.000000000000 0.000000000000 12.000000000000
O 0.000000000000 0.000000000000 -2.196050570000 15.994914619570
Running in d2h symmetry.
Rotational constants: A = ************ B = 0.39021 C = 0.39021 [cm^-1]
Rotational constants: A = ************ B = 11698.18105 C = 11698.18105 [MHz]
Nuclear repulsion = 58.286453758667307
Charge = 0
Multiplicity = 1
Electrons = 22
Nalpha = 11
Nbeta = 11
==> 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-08
==> Primary Basis <==
Basis Set: AUG-CC-PVTZ
Blend: AUG-CC-PVTZ
Number of shells: 42
Number of basis function: 138
Number of Cartesian functions: 165
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
=> Molecular Quadrature <=
Radial Scheme = TREUTLER
Pruning Scheme = FLAT
Nuclear Scheme = TREUTLER
BS radius alpha = 1
Pruning alpha = 1
Radial Points = 75
Spherical Points = 302
Total Points = 67950
Total Blocks = 594
Max Points = 256
Max Functions = 138
=> Loading Basis Set <=
Name: (AUG-CC-PVTZ AUX)
Role: JKFIT
Keyword: DF_BASIS_SCF
atoms 1, 3 entry O line 286 file /usr/local/psi4/share/psi4/basis/aug-cc-pvtz-jkfit.gbs
atoms 2 entry C line 162 file /usr/local/psi4/share/psi4/basis/aug-cc-pvtz-jkfit.gbs
==> Pre-Iterations <==
-------------------------------------------------------
Irrep Nso Nmo Nalpha Nbeta Ndocc Nsocc
-------------------------------------------------------
Ag 30 30 0 0 0 0
B1g 8 8 0 0 0 0
B2g 14 14 0 0 0 0
B3g 14 14 0 0 0 0
Au 7 7 0 0 0 0
B1u 27 27 0 0 0 0
B2u 19 19 0 0 0 0
B3u 19 19 0 0 0 0
-------------------------------------------------------
Total 138 138 11 11 11 0
-------------------------------------------------------
==> Integral Setup <==
DFHelper Memory: AOs need 0.050 GiB; user supplied 5.338 GiB. Using in-core AOs.
==> MemDFJK: Density-Fitted J/K Matrices <==
J tasked: Yes
K tasked: Yes
wK tasked: No
OpenMP threads: 6
Memory [MiB]: 5466
Algorithm: Core
Schwarz Cutoff: 1E-08
Mask sparsity (%): 0.2310
Fitting Condition: 1E-10
=> Auxiliary Basis Set <=
Basis Set: (AUG-CC-PVTZ AUX)
Blend: AUG-CC-PVTZ-JKFIT
Number of shells: 90
Number of basis function: 312
Number of Cartesian functions: 393
Spherical Harmonics?: true
Max angular momentum: 4
Cached 100.0% of DFT collocation blocks in 0.250 [GiB].
Minimum eigenvalue in the overlap matrix is 3.4919999955E-04.
Using Symmetric Orthogonalization.
SCF Guess: Superposition of Atomic Densities via on-the-fly atomic UHF.
==> Iterations <==
Total Energy Delta E RMS |[F,P]|
@DF-RKS iter SAD: -193.65505999068546 -1.93655e+02 0.00000e+00
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 4, 0, 1, 1, 0, 3, 1, 1 ]
@DF-RKS iter 1: -82.72623937759155 1.10929e+02 2.12202e-01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 5, 0, 1, 0, 0, 4, 0, 1 ]
@DF-RKS iter 2: -169.77301905817976 -8.70468e+01 2.72590e-01 DIIS
@DF-RKS iter 3: -691.50680729198166 -5.21734e+02 2.54102e+01 DIIS
@DF-RKS iter 4: -196.18808205872338 4.95319e+02 3.89882e+00 DIIS
@DF-RKS iter 5: -105.15909543468698 9.10290e+01 1.69359e+01 DIIS
@DF-RKS iter 6: -583.50494346248877 -4.78346e+02 5.07427e+01 DIIS
@DF-RKS iter 7: -552.80349855043198 3.07014e+01 2.02533e+00 DIIS
@DF-RKS iter 8: -484.62840934046704 6.81751e+01 4.90974e+00 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 4, 0, 1, 1, 0, 4, 0, 1 ]
@DF-RKS iter 9: -480.90360748547522 3.72480e+00 1.29184e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 4, 0, 1, 0, 0, 4, 1, 1 ]
@DF-RKS iter 10: -760.67028878671329 -2.79767e+02 1.72667e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 5, 0, 1, 0, 0, 4, 0, 1 ]
@DF-RKS iter 11: -875.58203036718976 -1.14912e+02 1.22873e+01 DIIS
@DF-RKS iter 12: -781.97605261568060 9.36060e+01 1.16342e+01 DIIS
@DF-RKS iter 13: -517.94856964410405 2.64027e+02 2.13046e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 4, 0, 1, 0, 0, 4, 1, 1 ]
@DF-RKS iter 14: -481.17516375602611 3.67734e+01 2.44152e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 5, 0, 1, 0, 0, 4, 0, 1 ]
@DF-RKS iter 15: -577.71506897349252 -9.65399e+01 2.73706e+01 DIIS
@DF-RKS iter 16: -978.51799708334067 -4.00803e+02 3.02588e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 4, 0, 1, 0, 0, 4, 1, 1 ]
@DF-RKS iter 17: -482.13708574470041 4.96381e+02 4.16479e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 5, 0, 1, 0, 0, 4, 0, 1 ]
@DF-RKS iter 18: -308.32266087927644 1.73814e+02 1.65591e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 4, 0, 1, 0, 0, 4, 1, 1 ]
@DF-RKS iter 19: -939.81534748010665 -6.31493e+02 1.97846e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 3, 0, 1, 1, 0, 4, 1, 1 ]
@DF-RKS iter 20: -2550.94293258592961 -1.61113e+03 2.93213e+01 DIIS
Occupation by irrep:
Ag B1g B2g B3g Au B1u B2u B3u
DOCC [ 5, 0, 1, 0, 0, 4, 0, 1 ]