[molpro-user] Unreasonable T2 norm for CCSD(T) calculation with cc-pCVTZ but not for cc-pCVDZ
Paul Jerabek
paul.jerabek at chemie.uni-marburg.de
Thu Feb 5 14:51:55 GMT 2015
Dear all,
I'm trying to calculate the core electron ionization energy for CO with
CCSD(T) including core-valence correlation. The problem arises with the
singly 1s(C) core-electron ionized CO molecule.
With a cc-pCVDT basis I get a nicely converged CCSD(T) result. When
using the larger basis cc-pCVTZ, the calculation stops with the
"unreasonable norm" error and a large value for the t2 norm vector.
Also: The MP2 part of the CCSD(T) calculation won't converge with the
cc-pCVTZ basis as well, although I overcame this obstacle by playing
around with the DIIS options: "diis, 1,1,6,1" worked for me.
Do you have any idea what exactly causes the problem at the cc-pCVTZ
level and how to deal with it this? I'd really like to get the energies
at the CCSD(T)/cc-pCVTZ level of theory.
Thank you very much for your help!!
Paul
- Inputs and outputs:
My cc-pCVTZ input:
basis=cc-pCVTZ
angstrom
geometry={
2
C 0.0000000000 0.0000000000 0.0000000
O 0.0000000000 0.000000000 -1.12800000
}
{hf;
WF, elec=13, sym=1, spin=1;
}
! The following creates the 1s(C) core hole:
{hf,nitord=1;
WF, elec=13, sym=1, spin=1;
rotate, 2.1,5.1,0;
open, 2.1;
}
{uccsd(t);core;}
Generating this output for the CCSD(T) part:
____________________________________________
1PROGRAM * CCSD (Unrestricted open-shell coupled cluster) Authors:
C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992
Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06
CCSD(T) terms to be evaluated (factor= 1.000)
Number of closed-shell orbitals: 6 ( 4 1 1 0 )
Number of active orbitals: 1 ( 1 0 0 0 )
Number of external orbitals: 79 ( 33 19 19 8 )
Memory could be reduced to 2.50 Mwords without degradation in triples
Number of N-1 electron functions: 13
Number of N-2 electron functions: 78
Number of singly external CSFs: 382
Number of doubly external CSFs: 108930
Total number of CSFs: 109312
Molecular orbitals read from record 2101.2 Type=RHF/CANONICAL
(state 1.1)
Integral transformation finished. Total CPU: 0.03 sec, npass= 1
Memory used: 0.30 MW
Starting RMP2 calculation
ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE
DEN1 VAR(S) VAR(P) DIIS TIME
1 1.26767668 -0.49403951 -102.35576095 -0.49403951
-0.00556325 0.11D-04 0.88D-01 1 1 0.04
2 1.24402423 -0.49386440 -102.35558584 0.00017510
-0.00474534 0.12D-04 0.75D-01 2 2 0.05
3 1.17062309 -0.49303741 -102.35475885 0.00082700
-0.00214434 0.47D-05 0.19D-01 3 3 0.05
4 1.19163131 -0.49336773 -102.35508917 -0.00033032
-0.00280304 0.37D-05 0.29D-01 4 4 0.06
5 1.14022363 -0.49331910 -102.35504054 0.00004862
-0.00008010 0.35D-06 0.78D-03 5 5 0.07
6 1.14287798 -0.49347226 -102.35519370 -0.00015315
-0.00016096 0.11D-06 0.15D-02 6 6 0.07
7 1.13954710 -0.49342221 -102.35514365 0.00005005
-0.00003111 0.15D-06 0.22D-03 6 1 0.08
8 1.13958229 -0.49353959 -102.35526103 -0.00011738
-0.00000080 0.92D-08 0.13D-03 6 6 0.08
9 1.14034754 -0.49350265 -102.35522409 0.00003694
-0.00001444 0.15D-08 0.25D-03 6 5 0.09
10 1.13949383 -0.49358308 -102.35530452 -0.00008043
-0.00000358 0.15D-08 0.20D-04 6 4 0.09
11 1.13948118 -0.49359562 -102.35531706 -0.00001254
-0.00000445 0.53D-09 0.35D-04 6 2 0.10
12 1.13955524 -0.49358821 -102.35530965 0.00000741
-0.00000303 0.18D-09 0.20D-04 6 3 0.10
13 1.13954808 -0.49359154 -102.35531298 -0.00000333
-0.00000306 0.97D-10 0.22D-04 6 1 0.11
14 1.13956163 -0.49358927 -102.35531071 0.00000227
-0.00000303 0.88D-10 0.23D-04 6 6 0.11
15 1.13954749 -0.49359911 -102.35532055 -0.00000983
-0.00000350 0.66D-10 0.33D-04 6 5 0.11
16 1.13957530 -0.49359128 -102.35531272 0.00000783
-0.00000292 0.40D-10 0.21D-04 6 4 0.12
17 1.13975404 -0.49356581 -102.35528725 0.00002547
-0.00000226 0.53D-10 0.90D-05 6 3 0.12
18 1.13969374 -0.49357987 -102.35530131 -0.00001406
-0.00000223 0.18D-10 0.13D-04 6 2 0.13
19 1.13981644 -0.49357693 -102.35529837 0.00000293
-0.00000248 0.11D-10 0.20D-04 6 4 0.14
20 1.13985209 -0.49356639 -102.35528782 0.00001055
-0.00000197 0.22D-10 0.70D-05 6 2 0.15
21 1.13967732 -0.49359340 -102.35531484 -0.00002702
-0.00000330 0.14D-10 0.37D-04 6 3 0.16
22 1.13978183 -0.49358187 -102.35530331 0.00001154
-0.00000266 0.18D-10 0.24D-04 6 2 0.16
23 1.13985227 -0.49356499 -102.35528643 0.00001688
-0.00000212 0.20D-10 0.72D-05 6 3 0.17
24 1.13968904 -0.49359119 -102.35531263 -0.00002620
-0.00000296 0.15D-10 0.30D-04 6 2 0.17
25 1.13977038 -0.49358362 -102.35530506 0.00000757
-0.00000278 0.17D-10 0.27D-04 6 3 0.18
26 1.13982646 -0.49356695 -102.35528839 0.00001667
-0.00000200 0.19D-10 0.69D-05 6 2 0.19
27 1.13969005 -0.49359153 -102.35531297 -0.00002458
-0.00000303 0.15D-10 0.32D-04 6 3 0.19
28 1.13976301 -0.49358524 -102.35530668 0.00000629
-0.00000296 0.17D-10 0.30D-04 6 2 0.20
29 1.13978672 -0.49357212 -102.35529356 0.00001313
-0.00000181 0.17D-10 0.60D-05 6 3 0.21
?CONVERGENCE NOT REACHED AFTER MAX. ITERATIONS
Spin contamination <S**2-Sz**2-Sz> 0.01026906
Reference energy -101.861721439818
RHF-RMP2 correlation energy -0.493572115599
!RHF-RMP2 energy -102.355293555417
Starting UCCSD calculation
ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE
DEN1 VAR(S) VAR(P) DIIS TIME
1 7.56966322 -0.48016065 -102.34188209 -0.48016065
-0.31678089 0.58D-02 0.61D+01 1 1 0.36
UNREASONABLE NORM. CALCULATION STOPPED
Norm of t1 vector: 0.09135834 S-energy: -0.00521914
T1 diagnostic: 0.01443667
D1 diagnostic: 0.03480135
Norm of t2 vector: 2.56150676 P-energy: -0.47494151
Alpha-Beta: -0.37116672
Alpha-Alpha: -0.04996811
Beta-Beta: -0.05380668
Doubles amplitudes (print threshold = 0.500E-01):
I J SYM. A SYM. B A B T(IJ,
AB) [Alpha-Alpha]
7 6 2 3 1 1 0.05116033
7 6 3 2 1 1 -0.05116033
I J SYM. A SYM. B A B T(IJ,
AB) [Beta-Beta]
3 2 1 1 1 21 0.11558142
3 2 1 1 21 1 -0.11558142
4 2 1 1 1 21 0.09454732
4 2 1 1 1 22 2.11412607
4 2 1 1 21 1 -0.09454732
4 2 1 1 22 1 -2.11412607
I J SYM. A SYM. B A B T(IJ,
AB) [Alpha-Beta]
3 2 1 1 21 1 0.21097982
3 2 1 1 22 1 0.05146041
2 3 1 1 21 1 0.29802902
2 3 1 1 22 1 0.07194777
4 2 1 1 22 1 0.26354643
2 4 1 1 21 1 0.06646343
2 4 1 1 22 1 1.31945707
6 6 2 2 1 1 -0.09221865
7 7 3 3 1 1 -0.09221865
7 6 3 2 1 1 -0.06479562
6 7 2 3 1 1 -0.06479562
?ERROR: NO CONVERGENCE. TRIPLES WILL NOT BE DONE. THIS CAN BE AVOIDED
USING THE NOCHECK OPTION.
Spin contamination <S**2-Sz**2-Sz> 0.08566146
Correlated core orbitals: 1.1 2.1
Orbital energies: -21.2251 -2.0818
UCCSD core-core energy -0.055641118427
UCCSD core-valence energy -0.112063864274
UCCSD valence correlation energy -0.312455667665
RESULTS
=======
Reference energy -101.861721439818
UCCSD singles energy -0.005219140527
UCCSD pair energy -0.474941509839
UCCSD correlation energy -0.480160650366
!RHF-UCCSD energy -102.341882090184
Program statistics:
Available memory in ccsd: 799999438
Min. memory needed in ccsd: 363878
Max. memory used in ccsd: 491028
Max. memory used in cckext: 437954 ( 1 integral passes)
Max. memory used in cckint: 302473 ( 1 integral passes)
? Error
? No convergence. This error exit can be avoided using the NOCHECK option
? The problem occurs in ccsd
____________________________________________
My cc-pCVDZ input is as follows:
basis=cc-pCVDZ
angstrom
geometry={
2
C 0.0000000000 0.0000000000 0.0000000
O 0.0000000000 0.000000000 -1.12800000
}
{hf;
WF, elec=13, sym=1, spin=1;
}
! The following creates the 1s(C) core hole:
{hf,nitord=1;
WF, elec=13, sym=1, spin=1;
rotate, 2.1,5.1,0;
open, 2.1;
}
{uccsd(t);core;}
Generating this output for the CCSD(T) part:
____________________________________________
1PROGRAM * CCSD (Unrestricted open-shell coupled cluster) Authors:
C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992
Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06
CCSD(T) terms to be evaluated (factor= 1.000)
Number of closed-shell orbitals: 6 ( 4 1 1 0 )
Number of active orbitals: 1 ( 1 0 0 0 )
Number of external orbitals: 29 ( 13 7 7 2 )
Memory could be reduced to 0.46 Mwords without degradation in triples
Number of N-1 electron functions: 13
Number of N-2 electron functions: 78
Number of singly external CSFs: 154
Number of doubly external CSFs: 16890
Total number of CSFs: 17044
Molecular orbitals read from record 2101.2 Type=RHF/CANONICAL
(state 1.1)
Integral transformation finished. Total CPU: 0.01 sec, npass= 1
Memory used: 0.10 MW
Starting RMP2 calculation
ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE
DEN1 VAR(S) VAR(P) DIIS TIME
1 1.12409217 -0.38855487 -102.17840478 -0.38855487
-0.00170845 0.11D-04 0.75D-03 1 1 0.01
2 1.12590721 -0.39038223 -102.18023214 -0.00182737
-0.00000500 0.11D-06 0.21D-05 2 2 0.01
3 1.12598549 -0.39044480 -102.18029471 -0.00006257
-0.00000003 0.15D-08 0.19D-07 3 3 0.01
4 1.12599306 -0.39045144 -102.18030135 -0.00000664
-0.00000000 0.21D-10 0.16D-09 4 4 0.01
5 1.12599334 -0.39045148 -102.18030139 -0.00000003
-0.00000000 0.21D-12 0.11D-11 5 5 0.01
Norm of t1 vector: 0.03516262 S-energy: -0.00321409
T1 diagnostic: 0.00027154
Norm of t2 vector: 0.35320947 P-energy: -0.38723739
Alpha-Beta: -0.29058556
Alpha-Alpha: -0.04917439
Beta-Beta: -0.04747745
Spin contamination <S**2-Sz**2-Sz> 0.00993509
Reference energy -101.789849910161
RHF-RMP2 correlation energy -0.390451477943
!RHF-RMP2 energy -102.180301388104
Starting UCCSD calculation
ITER. SQ.NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE
DEN1 VAR(S) VAR(P) DIIS TIME
1 1.11229466 -0.36958544 -102.15943535 -0.36958544
-0.01717517 0.42D-02 0.36D-02 1 1 0.03
2 1.12851095 -0.38441097 -102.17426088 -0.01482553
-0.00248284 0.26D-03 0.81D-03 2 2 0.06
3 1.13880762 -0.38898714 -102.17883705 -0.00457618
-0.00050990 0.11D-03 0.12D-03 3 3 0.08
4 1.14645710 -0.39199507 -102.18184498 -0.00300793
-0.00018231 0.27D-04 0.36D-04 4 4 0.10
5 1.15013310 -0.39273917 -102.18258908 -0.00074409
-0.00008220 0.32D-05 0.20D-04 5 5 0.12
6 1.15221476 -0.39315130 -102.18300121 -0.00041214
-0.00004124 0.21D-05 0.11D-04 6 6 0.15
7 1.15307829 -0.39342898 -102.18327889 -0.00027767
-0.00002168 0.40D-05 0.50D-05 6 1 0.18
8 1.15336241 -0.39346566 -102.18331557 -0.00003668
-0.00001331 0.32D-05 0.28D-05 6 3 0.20
9 1.15401855 -0.39372727 -102.18357718 -0.00026161
-0.00000572 0.67D-06 0.16D-05 6 2 0.22
10 1.15437935 -0.39378095 -102.18363086 -0.00005368
-0.00000179 0.11D-06 0.60D-06 6 5 0.24
11 1.15480576 -0.39385868 -102.18370859 -0.00007773
-0.00000043 0.98D-07 0.95D-07 6 4 0.26
12 1.15491062 -0.39385889 -102.18370881 -0.00000022
-0.00000019 0.48D-07 0.43D-07 6 6 0.29
13 1.15498805 -0.39386528 -102.18371519 -0.00000638
-0.00000006 0.75D-08 0.18D-07 6 1 0.31
14 1.15500282 -0.39386034 -102.18371025 0.00000494
-0.00000002 0.13D-08 0.47D-08 6 3 0.33
15 1.15500066 -0.39385580 -102.18370571 0.00000454
-0.00000001 0.34D-09 0.20D-08 6 2 0.36
16 1.15499853 -0.39385514 -102.18370505 0.00000066
-0.00000001 0.49D-09 0.18D-08 6 5 0.38
Norm of t1 vector: 0.12340148 S-energy: -0.00480873
T1 diagnostic: 0.01684129
D1 diagnostic: 0.03924278
Norm of t2 vector: 0.37385907 P-energy: -0.38904641
Alpha-Beta: -0.31570541
Alpha-Alpha: -0.03770254
Beta-Beta: -0.03563847
Singles amplitudes (print threshold = 0.500E-01):
I SYM. A A T(IA) [Alpha-Alpha]
6 2 1 0.06824784
7 3 1 0.06824784
Doubles amplitudes (print threshold = 0.500E-01):
I J SYM. A SYM. B A B T(IJ,
AB) [Alpha-Beta]
4 4 2 2 1 1 -0.05458637
4 4 3 3 1 1 -0.05458637
6 6 2 2 1 1 -0.12357167
7 7 3 3 1 1 -0.12357167
5 6 2 1 1 1 -0.05688095
5 7 3 1 1 1 -0.05688095
7 6 3 2 1 1 -0.07404280
6 7 2 3 1 1 -0.07404280
Spin contamination <S**2-Sz**2-Sz> 0.00671828
Memory could be reduced to 0.51 Mwords without degradation in triples
Correlated core orbitals: 1.1 2.1
Orbital energies: -21.2420 -2.0950
UCCSD core-core energy -0.044277318985
UCCSD core-valence energy -0.067552227320
UCCSD valence correlation energy -0.282025593229
RESULTS
=======
Reference energy -101.789849910161
UCCSD singles energy -0.004808728256
UCCSD pair energy -0.389046411278
UCCSD correlation energy -0.393855139534
Triples (T) contribution -0.014392247539
Total correlation energy -0.408247387073
RHF-UCCSD energy -102.183705049695
RHF-UCCSD[T] energy -102.199882100889
RHF-UCCSD-T energy -102.197637602862
!RHF-UCCSD(T) energy -102.198097297234
Program statistics:
Available memory in ccsd: 799999438
Min. memory needed in ccsd: 61788
Max. memory used in ccsd: 81128
Max. memory used in cckext: 112394 (16 integral passes)
Max. memory used in cckint: 98436 ( 1 integral passes)
____________________________________________
--
Dr. Paul Jerabek
Fachbereich Chemie, AK Berger, Theoretische Chemie
Philipps-Universität Marburg
Hans-Meerwein-Strasse
D-35032 Marburg
Germany
Phone: +49-(0)6421-28-27001
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