[molpro-user] problem in caspt2
Peterson, Kirk
kipeters at wsu.edu
Thu Aug 31 17:34:25 CEST 2017
Dear Basir,
your 2nd root is not converging (not even close). I would warrant to guess there is another state very close by or your active space is not sufficient to
describe this state. I’ve copied this to the whole list since others have more experience with this part of the program.
best,
-Kirk
Dear Molpro-users,
Thank you for your reply.
I have mentioned below both input and output file .
with regards.
Basir Ahamed Khan
-------------------------------------------------------------------
The input file is :
basis=aug-cc-pVTZ
ANGSTROM
geometry={
13
H 0.0000000000 0.0000000000 1.0764540290
C -1.3829489757 0.0000000000 -0.0235459710
C 1.3829489757 0.0000000000 -0.0235459710
C -0.7170426451 -1.2709157166 -0.0235459710
C -0.7170426451 1.2709157166 -0.0235459710
C 0.7170426451 -1.2709157166 -0.0235459710
C 0.7170426451 1.2709157166 -0.0235459710
H -2.4616327395 0.0000000000 0.0910251485
H 2.4616327395 0.0000000000 0.0910251485
H -1.2935012962 -2.1727274326 0.1062481643
H -1.2935012962 2.1727274326 0.1062481643
H 1.2935012962 -2.1727274326 0.1062481643
H 1.2935012962 2.1727274326 0.1062481643
}
set,nelec=42
hf
{multi;
closed,6,6,3,3;
occ,10,6,6,3;
wf;state,2
canonical,2140.2}
{rs2,mix=2;
wf,42,1,0;state,2}
---
and the output portion is:
-----------------------
PROGRAM * RS2 (Multireference RS Perturbation Theory) Authors: H.-J. Werner (1993), P. Celani (1998)
Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06
Number of optimized states: 2 Roots: 1 2
Number of reference states: 2 Roots: 1 2
Reference symmetry: 1 Singlet
Number of electrons: 42
Maximum number of shells: 7
Maximum number of spin couplings: 132
Reference space: 185 conf 254 CSFs
N elec internal: 32919 conf 86926 CSFs
N-1 el internal: 35204 conf 152194 CSFs
N-2 el internal: 17783 conf 116662 CSFs
Number of electrons in valence space: 30
Maximum number of open shell orbitals in reference space: 6
Maximum number of open shell orbitals in internal spaces: 12
Number of core orbitals: 6 ( 2 2 1 1 )
Number of closed-shell orbitals: 12 ( 4 4 2 2 )
Number of active orbitals: 7 ( 4 0 3 0 )
Number of external orbitals: 412 ( 116 114 91 91 )
Molecular orbitals read from record 2140.2 Type=MCSCF/CANONICAL (state averaged)
Coulomb and exchange operators available. No transformation done.
Number of p-space configurations: 5
Reference wavefunction optimized for reference space (refopt=1)
State Reference Energy
1 -230.97791702
2 -230.70029854
Number of blocks in overlap matrix: 8 Smallest eigenvalue: 0.40D-06
Number of N-2 electron functions: 722
Number of N-1 electron functions: 152194
Number of internal configurations: 21818
Number of singly external configurations: 15675246
Number of doubly external configurations: 15341674
Total number of contracted configurations: 31038738
Total number of uncontracted configurations: 2492489566
Weight factors for SA-density in H0: 0.500000 0.500000
FIMAX= 0.14D+00 FXMAX= 0.34D-08 DIAG= F F NOREF=1 NOINT=0 IHPPD=2
Nuclear energy: 210.64450737
Core energy: -295.56959098
Zeroth-order valence energy: -26.88731726 -26.39660481
Zeroth-order total energy: -111.81240088 -111.32168842
First-order energy: -119.16551614 -119.37861011
Using uncontracted singles
Diagonal Coupling coefficients finished. Storage: 931955 words, CPU-Time: 0.05 seconds.
Energy denominators for pairs finished in 0 passes. Storage: 1215250 words, CPU-time: 0.00 seconds.
ITER. STATE ROOT SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME
1 1 1 1.08142296 0.00000000 -230.97791702 0.00000000 -0.94569299 0.81D-01 0.25D+00 73.56
1 2 2 1.14442675 0.00000000 -230.70029854 0.00000000 -0.98910080 0.14D+00 0.25D+00 73.56
2 1 1 1.35117847 -0.97052923 -231.94844625 -0.97052923 -0.00235953 0.73D-03 0.94D-03 469.13
2 2 2 1.44824071 -1.03131837 -231.73161691 -1.03131837 -0.00339488 0.24D-02 0.10D-02 469.13
3 1 1 1.35652632 -0.97533440 -231.95325142 -0.00480518 -0.00310747 0.55D-04 0.12D-04 785.23
3 2 2 1.46100673 -1.03814867 -231.73844720 -0.00683030 -0.00366945 0.22D-03 0.16D-04 785.23
4 1 1 1.35707621 -0.97549405 -231.95341107 -0.00015965 -0.00002380 0.10D-05 0.16D-05 1103.35
4 2 2 1.46339910 -1.03839047 -231.73868900 -0.00024180 -0.00006723 0.81D-04 0.23D-05 1103.35
5 1 1 1.35730996 -0.97550146 -231.95341848 -0.00000741 -0.00010741 0.13D-06 0.34D-07 1419.89
5 2 2 1.46474724 -1.03841768 -231.73871622 -0.00002722 -0.00013863 0.71D-04 0.72D-07 1419.89
6 1 1 1.35733446 -0.97550187 -231.95341889 -0.00000041 -0.00000175 0.36D-08 0.55D-08 1638.15
6 2 2 1.46570218 -1.03843337 -231.73873191 -0.00001569 -0.00001185 0.83D-04 0.33D-07 1638.15
7 1 1 1.35734580 -0.97550190 -231.95341892 -0.00000003 -0.00000490 0.58D-09 0.16D-09 1887.73
7 2 2 1.46680465 -1.03845170 -231.73875023 -0.00001832 -0.00001443 0.12D-03 0.21D-07 1887.73
8 1 1 1.35734717 -0.97550190 -231.95341892 -0.00000000 -0.00000014 0.21D-10 0.30D-10 2201.71
8 2 2 1.46830773 -1.03847824 -231.73877678 -0.00002655 -0.00000763 0.18D-03 0.30D-07 2201.71
9 1 1 1.35734782 -0.97550190 -231.95341892 -0.00000000 -0.00000027 0.37D-11 0.12D-11 2516.52
9 2 2 1.47061044 -1.03852049 -231.73881903 -0.00004225 -0.00000780 0.30D-03 0.46D-07 2516.52
10 1 1 1.35734791 -0.97550190 -231.95341892 -0.00000000 -0.00000001 0.17D-12 0.22D-12 2833.21
10 2 2 1.47435128 -1.03859050 -231.73888904 -0.00007001 -0.00000780 0.51D-03 0.75D-07 2833.21
11 1 1 1.35734795 -0.97550190 -231.95341892 0.00000000 -0.00000002 0.30D-13 0.10D-13 3147.31
11 2 2 1.48061686 -1.03870842 -231.73900695 -0.00011792 -0.00000873 0.86D-03 0.13D-06 3147.31
12 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.16D-14 0.20D-14 3460.93
12 2 2 1.49125698 -1.03890838 -231.73920692 -0.00019997 -0.00001021 0.15D-02 0.21D-06 3460.93
13 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.27D-15 0.14D-15 3779.14
13 2 2 1.50942779 -1.03924829 -231.73954683 -0.00033991 -0.00001245 0.25D-02 0.36D-06 3779.14
14 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.16D-16 0.32D-16 4097.51
14 2 2 1.54051419 -1.03982670 -231.74012524 -0.00057841 -0.00001561 0.42D-02 0.62D-06 4097.51
15 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.24D-17 0.64D-17 4407.57
15 2 2 1.59370225 -1.04081138 -231.74110992 -0.00098468 -0.00002000 0.72D-02 0.11D-05 4407.57
16 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.27D-18 0.10D-17 4724.43
16 2 2 1.67974388 -1.04248806 -231.74278660 -0.00167668 -0.00002483 0.11D-01 0.18D-05 4724.43
17 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.62D-19 0.42D-18 5039.85
17 2 2 1.79159266 -1.04519201 -231.74549055 -0.00270395 -0.00002616 0.12D-01 0.28D-05 5039.85
18 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.20D-19 0.10D-18 5355.73
18 2 2 1.93344259 -1.04871138 -231.74900991 -0.00351936 -0.00002802 0.13D-01 0.31D-05 5355.73
19 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.20D-19 5675.40
19 2 2 2.11272301 -1.05317507 -231.75347360 -0.00446369 -0.00002950 0.16D-01 0.36D-05 5675.40
20 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 5992.41
20 2 2 2.34248357 -1.05882528 -231.75912382 -0.00565021 -0.00003156 0.20D-01 0.43D-05 5992.41
21 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 6310.90
21 2 2 2.61283784 -1.06608711 -231.76638565 -0.00726183 -0.00003290 0.20D-01 0.57D-05 6310.90
22 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 6629.01
22 2 2 2.92337014 -1.07463979 -231.77493832 -0.00855268 -0.00003300 0.20D-01 0.58D-05 6629.01
23 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 6930.61
23 2 2 3.27407886 -1.08446690 -231.78476544 -0.00982712 -0.00003298 0.20D-01 0.58D-05 6930.61
24 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 7123.99
24 2 2 3.66496404 -1.09556830 -231.79586684 -0.01110140 -0.00003295 0.20D-01 0.58D-05 7123.99
25 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 7439.83
25 2 2 4.09602634 -1.10794386 -231.80824240 -0.01237556 -0.00003292 0.20D-01 0.58D-05 7439.83
26 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 7671.06
26 2 2 4.56726623 -1.12159358 -231.82189212 -0.01364972 -0.00003290 0.20D-01 0.58D-05 7671.06
27 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 7938.30
27 2 2 5.07868413 -1.13651746 -231.83681599 -0.01492387 -0.00003288 0.20D-01 0.58D-05 7938.30
28 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 8212.17
28 2 2 5.63028041 -1.15271548 -231.85301402 -0.01619802 -0.00003287 0.20D-01 0.58D-05 8212.17
29 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 8495.87
29 2 2 6.22205535 -1.17018765 -231.87048619 -0.01747217 -0.00003286 0.20D-01 0.58D-05 8495.87
30 1 1 1.35734796 -0.97550190 -231.95341892 0.00000000 -0.00000000 0.00D+00 0.00D+00 8846.24
30 2 2 6.85400918 -1.18893398 -231.88923251 -0.01874632 -0.00003285 0.20D-01 0.58D-05 8846.24
Energy contributions for state 1.1:
===================================
Energy contr. SQ.Norm of FOWF
Space I -0.02650612 0.02285439
Space S -0.16604502 0.08512034
Space P -0.78295076 0.24937323
Energy contributions for state 2.1:
===================================
Energy contr. SQ.Norm of FOWF
Space I -0.04439339 0.05469264
Space S -0.37690625 5.54438098
Space P -0.76763434 0.25493555
?CI HAS NOT CONVERGED IN MAX ITERATIONS
=====================================
Analysis of CPU times by interactions
=====================================
I S P
I 0.2%
S 2.3% 3.7%
P 0.0% 90.8% 1.3%
Initialization: 0.5%
Other: 1.1%
Total CPU: 8846.2 seconds
=====================================
Initialize record 7000.1
*******************************************
* MS-CASPT2 analysis *
*******************************************
S final
1 2
1 1.3573480 0.0096599
2 0.0096599 6.8540092
Heff final
1 2
1 -231.9534189 0.0008154
2 0.0050610 -231.8892325
*******************************************
* Diagonalization of Heff *
* Unscaled effective Hamiltonian *
*******************************************
Heff Brandow symmetrized
1 2
1 -231.9534088 0.0058287
2 0.0058287 -231.8892427
MS-CASPT2 energies
STATE ENERGY MIXING COEFFICIENTS
1 -231.9539339 0.9960 -0.0897
2 -231.8887175 0.0897 0.9960
=====================================
Heff Half Sum symmetrized
1 2
1 -231.9534189 0.0029382
2 0.0029382 -231.8892325
MS-CASPT2 energies (unshifted)
STATE ENERGY MIXING COEFFICIENTS
1 -231.9535531 0.9990 -0.0456
2 -231.8890983 0.0456 0.9990
*******************************************
* End of MS-CASPT2 analysis *
* Properties not yet implemented *
*******************************************
Reference coefficients greater than 0.0500000
=============================================
2222200022222222022 0.9884378 -0.0122327
2222/\0022222222022 0.0085854 0.9761474
22222//0222222\\022 0.0171797 0.1114337
22222/\0222222/\022 0.0100175 0.1071051
22222200222222/\022 0.0089903 0.0858557
22222/\022222220022 -0.0833912 -0.0045701
2222202022222220022 -0.0753536 0.0060321
2222/\2022222220022 0.0005573 -0.0617510
Internal coefficients greater than 0.0500000
=============================================
222/\20022222222022 -0.0000927 0.1128762
22222//022\\2222022 -0.0098865 0.0862832
222/2\0022222222022 0.0839229 -0.0111166
222/20\022222222022 -0.0022642 -0.0740393
2222/\2022202222022 -0.0002542 -0.0617769
2222202022202222022 -0.0616247 0.0012723
22222/\022/\2222022 -0.0070944 0.0582187
Coefficients of singly external configurations greater than 0.0500000
=====================================================================
222220002222222\022 7.3 -0.0047021 -1.8412017
22222000222\2222022 7.2 0.0050488 1.4039580
2222200022222\22022 7.3 -0.0024417 -0.1074193
22222/00222\22\2022 4.4 -0.0036639 -0.0936879
222220002222\222022 7.3 -0.0015352 0.0885065
222220/0222\222\022 4.4 -0.0651159 0.0020724
222220\0222/222\022 4.4 -0.0643330 0.0018676
2222\/\0222/222\022 4.4 -0.0000738 -0.0615472
2222\//0222\222\022 4.4 -0.0002172 -0.0583523
22222\002/22222\022 4.4 -0.0015320 -0.0575831
22222\0022/2222\022 4.4 0.0142941 -0.0565975
222220002222222\022 8.3 0.0036673 -0.0559464
22222/00222\222\022 4.4 -0.0522143 -0.0013995
Coefficients of fixed reference functions:
==========================================
State Coefficients
1 1.000000 0.000000
2 0.000000 1.000000
Coefficients of rotated reference functions:
============================================
State Coefficients
1 1.000000 0.000000
2 0.000000 1.000000
RESULTS FOR STATE 1.1
=====================
Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) 1.00000000 (rotated)
Energy contributions of configuration classes
CLASS SQ.NORM ECORR1 ECORR2
+++++++++++++++++++++++++++++++++++++++++++++++++++
Internals 0.02285439 -0.02650612 0.92261658
Singles 0.08512034 -0.16604502 -0.33213574
Pairs 0.24937323 -0.78295075 -1.56611696
Total 1.35734796 -0.97550189 -0.97563612
+++++++++++++++++++++++++++++++++++++++++++++++++++
Reference energy -230.97791702
Nuclear energy 210.64450737
Kinetic energy 230.82144006
One electron energy -718.16636550
Two electron energy 275.56830500
Virial quotient -1.00490471
Correlation energy -0.97563612
!RSPT2 STATE 1.1 Energy -231.953553134506
Properties without orbital relaxation:
!RSPT2 STATE 1.1 Dipole moment 0.00000000 0.00000000 0.59918422
Dipole moment /Debye 0.00000000 0.00000000 1.52287462
RESULTS FOR STATE 2.1
=====================
Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) 1.00000000 (rotated)
Energy contributions of configuration classes
CLASS SQ.NORM ECORR1 ECORR2
+++++++++++++++++++++++++++++++++++++++++++++++++++
Internals 0.05469264 -0.04439340 0.94998327
Singles 5.54438098 -0.22693318 -0.60377126
Pairs 0.25493555 -0.76755074 -1.53501177
Total 6.85400918 -1.03887732 -1.18879976
+++++++++++++++++++++++++++++++++++++++++++++++++++
Reference energy -230.70029854
Nuclear energy 210.64450737
Kinetic energy 229.72692679
One electron energy -712.47725205
Two electron energy 269.94364639
Virial quotient -1.00941192
Correlation energy -1.18879976
!RSPT2 STATE 2.1 Energy -231.889098297841
Properties without orbital relaxation:
!RSPT2 STATE 2.1 Dipole moment 0.00000000 0.00000000 0.31181803
Dipole moment /Debye 0.00000000 0.00000000 0.79251047
!RSPT overlap <2.1||1.1> 0.003167004575
!RSPT trans <2.1|DMZ|1.1> -0.362581398851 au = -0.921529631692 Debye
? Error
? No convergence. This error exit can be avoided using the NOCHECK option
? The problem occurs in cipro
------------------------
________________________________
From: Peterson, Kirk <kipeters at wsu.edu<mailto:kipeters at wsu.edu>>
Sent: Thursday, August 31, 2017 3:03 PM
To: KhanBasir Ahamed (자연과학부)
Cc: molpro-user molpro-user
Subject: Re: [molpro-user] problem in caspt2
Could you post all of the caspt2 part of the output to the list? It is impossible to see what might be going on from what you’ve given.
regards,
-Kirk
On Aug 30, 2017, at 9:38 AM, KhanBasir Ahamed (자연과학부) <bakhan at unist.ac.kr<mailto:bakhan at unist.ac.kr>> wrote:
Dear Molpro-users,
I would like to calculate the CASPT2 of a ion-molecule complex.
Let say, my system comprises with benzene and proton (C6H6,p) like as:
________________________________________________________________
basis=aug-cc-pVTZ
ANGSTROM
geometry={
13
H 0.0000000000 0.0000000000 1.0764540290
C -1.3829489757 0.0000000000 -0.0235459710
C 1.3829489757 0.0000000000 -0.0235459710
C -0.7170426451 -1.2709157166 -0.0235459710
C -0.7170426451 1.2709157166 -0.0235459710
C 0.7170426451 -1.2709157166 -0.0235459710
C 0.7170426451 1.2709157166 -0.0235459710
H -2.4616327395 0.0000000000 0.0910251485
H 2.4616327395 0.0000000000 0.0910251485
H -1.2935012962 -2.1727274326 0.1062481643
H -1.2935012962 2.1727274326 0.1062481643
H 1.2935012962 -2.1727274326 0.1062481643
H 1.2935012962 2.1727274326 0.1062481643
}
set,nelec=42
hf
{multi;
closed,6,6,3,3;
occ,10,6,6,3;
wf;state,2
canonical,2140.2}
{rs2,mix=2;
wf;state,2}
__________________________________________________________________
But it shows error. For your convenience I copied and paste the last portion of output file.
I would be glad if anyone can help for this problem.
With regards,
Basir Ahamed Khan
RESULTS FOR STATE 1.1
=====================
Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) 1.00000000 (rotated)
Energy contributions of configuration classes
CLASS SQ.NORM ECORR1 ECORR2
+++++++++++++++++++++++++++++++++++++++++++++++++++
Internals 0.02285439 -0.02650612 0.92261658
Singles 0.08512034 -0.16604502 -0.33213574
Pairs 0.24937323 -0.78295075 -1.56611696
Total 1.35734796 -0.97550189 -0.97563612
+++++++++++++++++++++++++++++++++++++++++++++++++++
Reference energy -230.97791702
Nuclear energy 210.64450737
Kinetic energy 230.82144006
One electron energy -718.16636550
Two electron energy 275.56830500
Virial quotient -1.00490471
Correlation energy -0.97563612
!RSPT2 STATE 1.1 Energy -231.953553134590
Properties without orbital relaxation:
!RSPT2 STATE 1.1 Dipole moment 0.00000000 0.00000000 0.59918422
Dipole moment /Debye 0.00000000 0.00000000 1.52287462
RESULTS FOR STATE 2.1
=====================
Coefficient of reference function: C(0) = 1.00000000 (fixed) 1.00000000 (relaxed) 1.00000000 (rotated)
Energy contributions of configuration classes
CLASS SQ.NORM ECORR1 ECORR2
+++++++++++++++++++++++++++++++++++++++++++++++++++
Internals 0.05469264 -0.04439341 0.94998327
Singles 5.54438085 -0.22693318 -0.60377126
Pairs 0.25493555 -0.76755074 -1.53501177
Total 6.85400905 -1.03887732 -1.18879976
+++++++++++++++++++++++++++++++++++++++++++++++++++
Reference energy -230.70029854
Nuclear energy 210.64450737
Kinetic energy 229.72692680
One electron energy -712.47725207
Two electron energy 269.94364640
Virial quotient -1.00941192
Correlation energy -1.18879976
!RSPT2 STATE 2.1 Energy -231.889098300045
Properties without orbital relaxation:
!RSPT2 STATE 2.1 Dipole moment 0.00000000 0.00000000 0.31181804
Dipole moment /Debye 0.00000000 0.00000000 0.79251051
!RSPT overlap <2.1||1.1> 0.003167004374
!RSPT trans <2.1|DMZ|1.1> -0.362581392446 au = -0.921529615414 Debye
? Error
? No convergence. This error exit can be avoided using the NOCHECK option
? The problem occurs in cipro
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