[molpro-user] NaN trouble with dft gradient
Bastiaan J. Braams
braams at mathcs.emory.edu
Sun Oct 5 23:23:03 BST 2008
Dear Molpro User,
I think that this is a bug report, but don't know where else to turn.
With use of Molpro 2006.1 and 2006.2 I have been computing DFT
gradients (Handy's hcth147 functional), and quite often not-a-number's
are returned for the gradient even when the energy and dipole
evaluation appear fine. Here is an example input that shows the
problem. The calculation takes a few minutes.
***, avtz/rks,hcth147 e+props for neutral doublet
memory,84,m
punch,mp.pun,new
geomtyp=xyz
geometry
nosym
5
-115.05839829
H -0.97570848 0.26905852 -1.07039074
H -0.51672095 -1.33018474 0.09699630
H 0.77243074 0.26018653 1.07055814
C -0.29477390 -0.38499258 -0.52291112
O 0.36830940 0.56612278 0.10654505
end
gexpec,dm,qm
basis=aug-cc-pvtz,li=cc-pvtz,be=cc-pvtz
{rks,hcth147;wf,charge=0,spin=1}
force
---
The geometry looks quite ordinary for CH2OH; it is close to the
minimum energy configuration, but not quite planar, and so not having
any accidental symmetry that might confuse matters.
Here is the punch file output (stripping out some blank lines):
*** avtz/r ks,hcth1 47 e+pro ps for n eutral d oublet
TIME 5-Oct-0 17:42:06
ATOM 1 H 1.00 -1.84382167 0.50844688 -2.02274520
ATOM 2 H 1.00 -0.97646101 -2.51368467 0.18329643
ATOM 3 H 1.00 1.45968244 0.49168125 2.02306154
ATOM 4 C 6.00 -0.55704190 -0.72753048 -0.98815873
ATOM 5 O 8.00 0.69600385 1.06981693 0.20134095
RKS STATE 1.1 ENERGY -115.05839829
RKS STATE 1.1 DIPOLE MOM 0.03595023 -0.19703358 0.67277530
RKS STATES 1.1 1.1 MATR.EL. FOR OPER. QMXX -0.13628380 COORD: 0.00000000 0.00000000 0.00000000
RKS STATES 1.1 1.1 MATR.EL. FOR OPER. QMYY -1.04294090 COORD: 0.00000000 0.00000000 0.00000000
RKS STATES 1.1 1.1 MATR.EL. FOR OPER. QMZZ 1.17922470 COORD: 0.00000000 0.00000000 0.00000000
RKS STATES 1.1 1.1 MATR.EL. FOR OPER. QMXY -0.29038812 COORD: 0.00000000 0.00000000 0.00000000
RKS STATES 1.1 1.1 MATR.EL. FOR OPER. QMXZ 2.23742023 COORD: 0.00000000 0.00000000 0.00000000
RKS STATES 1.1 1.1 MATR.EL. FOR OPER. QMYZ -1.07064143 COORD: 0.00000000 0.00000000 0.00000000
RKS STATES 1.1 1.1 MATR.EL. FOR OPER. QMRR -28.83127548 COORD: 0.00000000 0.00000000 0.00000000
VARIABLE HX1 -0.18438217E+01 BOHR
VARIABLE HY1 0.50844688E+00 BOHR
VARIABLE HZ1 -0.20227452E+01 BOHR
VARIABLE HX2 -0.97646101E+00 BOHR
VARIABLE HY2 -0.25136847E+01 BOHR
VARIABLE HZ2 0.18329643E+00 BOHR
VARIABLE HX3 0.14596824E+01 BOHR
VARIABLE HY3 0.49168125E+00 BOHR
VARIABLE HZ3 0.20230615E+01 BOHR
VARIABLE CX4 -0.55704190E+00 BOHR
VARIABLE CY4 -0.72753048E+00 BOHR
VARIABLE CZ4 -0.98815873E+00 BOHR
VARIABLE OX5 0.69600385E+00 BOHR
VARIABLE OY5 0.10698169E+01 BOHR
VARIABLE OZ5 0.20134095E+00 BOHR
RKS GRADIENT, ATOM 1: NaN NaN NaN
RKS GRADIENT, ATOM 2: NaN NaN NaN
RKS GRADIENT, ATOM 3: NaN NaN NaN
RKS GRADIENT, ATOM 4: NaN NaN NaN
RKS GRADIENT, ATOM 5: NaN NaN NaN
---
Below the next short line is the full output file. I suspect that the
line that says
DFT GRADIENT, EXFAC= 0.000
points to something that isn't right and that leads to computation of
0.0/0.0. Then the issue is what causes EXFAC to acquire this value.
Bas Braams
-------
Primary working directories: /var/scratch/braams
Secondary working directories: /var/scratch/braams
CPU=Opteron 2200.041:2200.041:2200.041:2200.041 MHz
Using default tuning parameters for linux_unknown
mxmblk= 64 mxmbln= 64 ncache=131072 mindgm= 32 mindgv= 32 mindgc= 24 mindgl= 8 mindgr= 4 noblas=0 nroll=2 minvec=7
default implementation of scratch files=df
***,avtz/rks,hcth147 e+props for neutral doublet
memory,84,m
punch,mp.pun,new
geomtyp=xyz
geometry
nosym
5
-115.05839829
H -0.97570848 0.26905852 -1.07039074
H -0.51672095 -1.33018474 0.09699630
H 0.77243074 0.26018653 1.07055814
C -0.29477390 -0.38499258 -0.52291112
O 0.36830940 0.56612278 0.10654505
end
gexpec,dm,qm
basis=aug-cc-pvtz,li=cc-pvtz,be=cc-pvtz
{rks,hcth147;wf,charge=0,spin=1}
force
---
Variables initialized (522), CPU time= 0.01 sec
Commands initialized (294), CPU time= 0.02 sec, 434 directives.
Default parameters read. Elapsed time= 0.05 sec
Checking input...
Passed
1
*** PROGRAM SYSTEM MOLPRO ***
Copyright, University College Cardiff Consultants Limited, 2004
Version 2006.2 linked 19 Sep 2005 03:08:13
**********************************************************************************************************************************
LABEL * avtz/rks,hcth147 e+props for neutral doublet
Linux-2.6.9-42.0.8.ELsmp/node016(x86_64) 64 bit version (path2.1) DATE: 5-Oct-08 TIME: 17:42:06
**********************************************************************************************************************************
Patch level: 113
**********************************************************************************************************************************
PUNCHFILE MP.PUN OPENED
SETTING GEOMTYP = XYZ
Variable memory set to 84000000 words, buffer space 230000 words
SETTING BASIS = AUG-CC-PVTZ
Recomputing integrals since basis changed
Using spherical harmonics
Library entry H S aug-cc-pVTZ selected for orbital group 1
Library entry H P aug-cc-pVTZ selected for orbital group 1
Library entry H D aug-cc-pVTZ selected for orbital group 1
Library entry C S aug-cc-pVTZ selected for orbital group 2
Library entry C P aug-cc-pVTZ selected for orbital group 2
Library entry C D aug-cc-pVTZ selected for orbital group 2
Library entry C F aug-cc-pVTZ selected for orbital group 2
Library entry O S aug-cc-pVTZ selected for orbital group 3
Library entry O P aug-cc-pVTZ selected for orbital group 3
Library entry O D aug-cc-pVTZ selected for orbital group 3
Library entry O F aug-cc-pVTZ selected for orbital group 3
1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990
Geometry written to block 1 of record 700
Point group C1
ATOMIC COORDINATES
NR ATOM CHARGE X Y Z
1 H 1.00 -1.843821672 0.508446878 -2.022745199
2 H 1.00 -0.976461008 -2.513684673 0.183296429
3 H 1.00 1.459682444 0.491681248 2.023061539
4 C 6.00 -0.557041900 -0.727530484 -0.988158733
5 O 8.00 0.696003845 1.069816930 0.201340950
Bond lengths in Bohr (Angstrom)
1-4 2.062477000 2-4 2.176824837 3-5 2.058181667 4-5 2.493088619
(1.091415905) (1.151926179) (1.089142913) (1.319285777)
Bond angles
1-4-2 129.90054381 1-4-5 96.94284791 2-4-5 115.57083736 3-5-4 113.97177613
NUCLEAR CHARGE: 17
NUMBER OF PRIMITIVE AOS: 215
NUMBER OF SYMMETRY AOS: 191
NUMBER OF CONTRACTIONS: 161 ( 161A )
NUMBER OF CORE ORBITALS: 2 ( 2A )
NUMBER OF VALENCE ORBITALS: 11 ( 11A )
NUCLEAR REPULSION ENERGY 35.42050309
Eigenvalues of metric
1 0.101E-03 0.132E-03 0.263E-03 0.470E-03 0.705E-03 0.839E-03 0.118E-02 0.151E-02
Contracted 2-electron integrals neglected if value below 1.0E-11
AO integral compression algorithm 1 Integral accuracy 1.0E-11
444.858 MB (compressed) written to integral file ( 53.2%)
NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 85040361. BUFFER LENGTH: 32768
NUMBER OF SEGMENTS: 6 SEGMENT LENGTH: 15999503 RECORD LENGTH: 524288
Memory used in sort: 16.56 MW
SORT1 READ 104548810. AND WROTE 83870001. INTEGRALS IN 243 RECORDS. CPU TIME: 2.60 SEC, REAL TIME: 6.32 SEC
SORT2 READ 83870001. AND WROTE 85040361. INTEGRALS IN 1697 RECORDS. CPU TIME: 3.00 SEC, REAL TIME: 5.33 SEC
FILE SIZES: FILE 1: 447.7 MBYTE, FILE 4: 1019.2 MBYTE, TOTAL: 1466.9 MBYTE
OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000
OPERATOR QM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 373.63 500 610 700 900 950 970 1000 1100 1400 1410
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS S T V
1200 1210 1080 1600 129 960 1650 1300 1700
H0 H01 AOSYM SMH P2S ABASIS MOLCAS ERIS OPER
PROGRAMS * TOTAL INT
CPU TIMES * 17.64 17.50
REAL TIME * 57.81 SEC
DISK USED * 1.47 GB
**********************************************************************************************************************************
Functional: HCTH147(Automatically generated HCTH147) Gradient terms: 1
Use grid at 1800.2
Functional: HCTH147 Factor: 1.0000
Generated new metagrid on record 1800.2 with target accuracy 1.0E-06 and 18072 points in CPU time 0.3
Computed new grid on record 1800.1 in CPU time 0.4
132324 words reserved for DFT integration
PROGRAM * RKS-SCF (Restricted open shell Kohn-Sham) Authors: W. Meyer, H.-J. Werner, P.J. Knowles, 1993
NUMBER OF ELECTRONS: 9+ 8- SPACE SYMMETRY=1 SPIN SYMMETRY=Doublet
CONVERGENCE THRESHOLDS: 1.00E-06 (Density) 1.00E-07 (Energy)
MAX. NUMBER OF ITERATIONS: 60
INTERPOLATION TYPE: DIIS
INTERPOLATION STEPS: 2 (START) 1 (STEP)
LEVEL SHIFTS: -0.30 (CLOSED) 0.00 (OPEN)
Density guess generated from atomic densities. Occupancy: 9
Molecular orbital dump at record 2100.2
ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS
Generated new metagrid on record 1801.2 with target accuracy 1.0E-03 and 2762 points in CPU time 0.1
Computed new grid on record 1801.1 in CPU time 0.1
1 0.000E+00 0.000E+00 -114.78417574 177.676790 0.000000 0.000000 0.000000 0
2 0.000E+00 0.234E-01 -114.97901757 187.810510 0.147070 -0.353039 1.202811 0
3 0.283E-01 0.491E-02 -114.55722129 166.342304 -1.467959 0.112544 -3.637341 1
4 0.249E-01 0.110E-01 -114.62493077 196.070425 -0.054495 -0.674951 1.565185 1
5 0.324E-01 0.131E-01 -115.04020265 183.898218 0.131715 -0.148804 1.061145 2
6 0.146E-01 0.208E-02 -115.05547769 182.669975 0.050288 -0.242086 0.737977 3
7 0.319E-02 0.108E-02 -115.05815180 182.141615 0.047909 -0.177072 0.709258 4
8 0.122E-02 0.196E-03 -115.05838182 181.995449 0.044368 -0.192071 0.679721 5
Selecting fine grid and restarting DIIS
Use fine grid record 1800.2 for energy threshold 1.0E-06
9 0.383E-03 0.424E-04 -115.05756678 181.999065 0.040927 -0.193262 0.669378 6
10 0.129E-03 0.399E-03 -115.05834990 182.041860 0.034293 -0.195200 0.673924 1
11 0.379E-02 0.815E-04 -115.05838986 182.026812 0.034807 -0.198506 0.671450 2
12 0.986E-03 0.455E-04 -115.05839651 182.029963 0.035766 -0.195574 0.673515 3
13 0.131E-03 0.169E-04 -115.05839799 182.043763 0.035650 -0.197410 0.673126 4
14 0.101E-03 0.828E-05 -115.05839823 182.035036 0.035853 -0.196958 0.672791 5
15 0.197E-04 0.182E-05 -115.05839828 182.035969 0.035905 -0.196977 0.672830 6
16 0.113E-04 0.421E-06 -115.05839829 182.036061 0.035951 -0.197033 0.672775 7
17 0.182E-05 0.166E-06 -115.05839829 182.036083 0.035943 -0.197034 0.672780 8
18 0.894E-06 0.101E-06 -115.05839829 182.036039 0.035950 -0.197034 0.672775 0
Final alpha occupancy: 9
Final beta occupancy: 8
!RKS STATE 1.1 ENERGY -115.058398286786
Nuclear energy 35.42050309
One-electron energy -226.47410147
Two-electron energy 91.01801926
Density functional -15.02281916 HCTH147=-15.02281916
Virial quotient -1.00715248
!RKS STATE 1.1 DIPOLE MOMENT 0.03595023 -0.19703358 0.67277530
Dipole moment /Debye 0.09137038 -0.50077660 1.70991224
!RKS expec <1.1|QMXX|1.1> -0.136283796910
!RKS expec <1.1|QMYY|1.1> -1.042940898648
!RKS expec <1.1|QMZZ|1.1> 1.179224695557
!RKS expec <1.1|QMXY|1.1> -0.290388116127
!RKS expec <1.1|QMXZ|1.1> 2.237420227292
!RKS expec <1.1|QMYZ|1.1> -1.070641426733
!RKS expec <1.1|QMRR|1.1> -28.831275482739
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 374.21 500 610 700 900 950 970 1000 1100 1400 1410
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS S T V
1200 1210 1080 1600 129 960 1650 1300 1700 1800
H0 H01 AOSYM SMH P2S ABASIS MOLCAS ERIS OPER GRID
2 5 1.23 700 1000 1800 1801 2100
GEOM BASIS GRID GRID RKS
PROGRAMS * TOTAL RKS INT
CPU TIMES * 107.12 89.48 17.50
REAL TIME * 153.33 SEC
DISK USED * 1.47 GB
**********************************************************************************************************************************
*** Long output written to logfile /home/braams/play/mp.log ***
1PROGRAM * ALASKA (Gradient of the energy) Author: R. Lindh
Orbitals from record 2100.2
Number of closed-shell orbitals: 8 ( 8 )
Number of active orbitals: 1 ( 1 )
Number of occupied orbitals: 9 ( 9 )
Number of electrons= 17 Doublet Space symmetry=1 Wavefunction type: OSCF
DFT GRADIENT, EXFAC= 0.000
RKS GRADIENT FOR STATE 1.1
Atom dE/dx dE/dy dE/dz
1 NaN NaN NaN
2 NaN NaN NaN
3 NaN NaN NaN
4 NaN NaN NaN
5 NaN NaN NaN
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 21 374.22 500 610 700 900 950 970 1000 1100 1400 1410
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS S T V
1200 1210 1080 1600 129 960 1650 1300 1700 1800
H0 H01 AOSYM SMH P2S ABASIS MOLCAS ERIS OPER GRID
701
GEOM
2 6 1.66 700 1000 1800 1801 2100 701
GEOM BASIS GRID GRID RKS GEOM
PROGRAMS * TOTAL FORCE RKS INT
CPU TIMES * 174.49 67.36 89.48 17.50
REAL TIME * 222.09 SEC
DISK USED * 1.47 GB
**********************************************************************************************************************************
RKS-SCF
-115.05839829
**********************************************************************************************************************************
Variable memory released
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