Hello,
I’ve come across cases where CCSD calculations on fairly small molecules diverge wildly, and the calculations end up with MP2 energies. For example, SP on acetone is fine with cc-pVDZ but not with cc-pVTZ.
Am I doing something wrong or is it just the way things are?
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Please cite Q-Chem as follows:
Y. Shao et al., Mol. Phys. 113, 184-215 (2015)
DOI: 10.1080/00268976.2014.952696
Q-Chem 5.4.0 for Intel X86 EM64T Linux
Parts of Q-Chem use Armadillo 9.800.1 (Horizon Scraper).
http://arma.sourceforge.net/
Q-Chem begins on Fri Aug 12 15:14:19 2022
Host:
0
Scratch files written to /somepath/
Processing $rem in /somepath/qchem.20210325/config/preferences:
Processing $rem in /somepath/:
Core orbitals will be frozen
Checking the input file for inconsistencies... ...done.
--------------------------------------------------------------
User input:
--------------------------------------------------------------
$rem
METHOD CCSD(T)
JOBTYPE SP
BASIS cc-pVTZ
$end
$molecule
0 1
C -2.50154040248934 1.94130075676444 -0.02248358320146
O -1.38277650374024 2.39049754028746 -0.01198270966319
C -2.81848423251740 0.62291698877755 -0.67970279571791
C -3.65209505348638 2.66878046299721 0.62371531767802
H -3.30363620087669 3.59656976406576 1.06677387032028
H -4.10959097717150 2.04207559163931 1.39023291904063
H -4.42500431777946 2.88017266963735 -0.11629234959823
H -1.91633754071756 0.19214490436456 -1.10295330529289
H -3.56329502268127 0.76358654290276 -1.46408231118147
H -3.25032974854015 -0.06538522143640 0.04790494761624
$end
--------------------------------------------------------------
----------------------------------------------------------------
Standard Nuclear Orientation (Angstroms)
I Atom X Y Z
----------------------------------------------------------------
1 C -2.5015404025 1.9413007568 -0.0224835832
2 O -1.3827765037 2.3904975403 -0.0119827097
3 C -2.8184842325 0.6229169888 -0.6797027957
4 C -3.6520950535 2.6687804630 0.6237153177
5 H -3.3036362009 3.5965697641 1.0667738703
6 H -4.1095909772 2.0420755916 1.3902329190
7 H -4.4250043178 2.8801726696 -0.1162923496
8 H -1.9163375407 0.1921449044 -1.1029533053
9 H -3.5632950227 0.7635865429 -1.4640823112
10 H -3.2503297485 -0.0653852214 0.0479049476
----------------------------------------------------------------
Nuclear Repulsion Energy = 119.96460455 hartrees
There are 16 alpha and 16 beta electrons
Requested basis set is cc-pVTZ
There are 76 shells and 204 basis functions
Total memory of 2000 MB is distributed as follows:
MEM_STATIC is set to 192 MB
QALLOC/CCMAN JOB total memory use is 1808 MB
Warning: actual memory use might exceed 2000 MB
Total QAlloc Memory Limit 2000 MB
Mega-Array Size 188 MB
MEM_STATIC part 192 MB
Distance Matrix (Angstroms)
C ( 1) O ( 2) C ( 3) C ( 4) H ( 5) H ( 6)
O ( 2) 1.205620
C ( 3) 1.506827 2.373067
C ( 4) 1.506843 2.373049 2.565027
H ( 5) 2.137699 2.511579 3.482551 1.085595
H ( 6) 2.142837 3.085956 2.822340 1.090693 1.780629
H ( 7) 2.142427 3.083150 2.827285 1.090728 1.780544 1.752573
H ( 8) 2.137621 2.511505 1.085622 3.482522 4.268773 3.801129
H ( 9) 2.143021 3.083844 1.090771 2.827817 3.807683 3.174916
H ( 10) 2.142995 3.085888 1.090717 2.822877 3.801427 2.642265
H ( 7) H ( 8) H ( 9)
H ( 8) 3.806889
H ( 9) 2.653115 1.780289
H ( 10) 3.175395 1.780543 1.752497
A cutoff of 1.0D-14 yielded 2888 shell pairs
There are 21028 function pairs ( 26828 Cartesian)
Smallest overlap matrix eigenvalue = 6.92E-04
Scale SEOQF with 1.000000e-01/1.000000e-01/1.000000e-01
Standard Electronic Orientation quadrupole field applied
Nucleus-field energy = 0.0000000178 hartrees
Guess from superposition of atomic densities
Warning: Energy on first SCF cycle will be non-variational
SAD guess density has 32.000000 electrons
-----------------------------------------------------------------------
General SCF calculation program by
Eric Jon Sundstrom, Paul Horn, Yuezhi Mao, Dmitri Zuev, Alec White,
David Stuck, Shaama M.S., Shane Yost, Joonho Lee, David Small,
Daniel Levine, Susi Lehtola, Hugh Burton, Evgeny Epifanovsky,
Bang C. Huynh
-----------------------------------------------------------------------
Hartree-Fock
A restricted SCF calculation will be
performed using DIIS
SCF converges when DIIS error is below 1.0e-08
---------------------------------------
Cycle Energy DIIS error
---------------------------------------
1 -193.0667059155 3.54e-02
2 -191.9342292412 4.34e-03
3 -191.9930514987 3.35e-03
4 -192.0323358565 4.44e-04
5 -192.0342265997 1.31e-04
6 -192.0344244091 5.23e-05
7 -192.0344632660 2.28e-05
8 -192.0344692676 6.38e-06
9 -192.0344698169 1.11e-06
10 -192.0344698327 3.40e-07
11 -192.0344698338 5.08e-08
12 -192.0344698339 7.30e-09 Convergence criterion met
---------------------------------------
SCF time: CPU 79.03s wall 80.00s
SCF energy in the final basis set = -192.0344698339
Total energy in the final basis set = -192.0344698339
------------------------------------------------------------------------------
CCMAN2: suite of methods based on coupled cluster
and equation of motion theories.
Components:
* libvmm-1.3-trunk
by Evgeny Epifanovsky, Ilya Kaliman.
* libtensor-2.5-trunk
by Evgeny Epifanovsky, Michael Wormit, Dmitry Zuev, Sam Manzer,
Ilya Kaliman.
* libcc-2.5-trunk
by Evgeny Epifanovsky, Arik Landau, Tomasz Kus, Kirill Khistyaev,
Dmitry Zuev, Prashant Manohar, Xintian Feng, Anna Krylov,
Matthew Goldey, Alec White, Thomas Jagau, Kaushik Nanda,
Anastasia Gunina, Alexander Kunitsa, Joonho Lee.
CCMAN original authors:
Anna I. Krylov, C. David Sherrill, Steven R. Gwaltney,
Edward F. C. Byrd (2000)
Sergey V. Levchenko, Lyudmila V. Slipchenko, Tao Wang,
Ana-Maria C. Cristian (2003)
Piotr A. Pieniazek, C. Melania Oana, Evgeny Epifanovsky (2007)
Prashant Manohar (2009)
------------------------------------------------------------------------------
Allocating and initializing 1808MB of RAM...
Calculation will run on 1 core.
Occupation and symmetry of molecular orbitals
Point group: C1 (1 irreducible representation).
A All
-------------------------------------
All molecular orbitals:
- Alpha 204 204
- Beta 204 204
-------------------------------------
Alpha orbitals:
- Frozen occupied 4 4
- Active occupied 12 12
- Active virtual 188 188
- Frozen virtual 0 0
-------------------------------------
Beta orbitals:
- Frozen occupied 4 4
- Active occupied 12 12
- Active virtual 188 188
- Frozen virtual 0 0
-------------------------------------
Import integrals: CPU 0.00 s wall 0.00 s
Import integrals: CPU 116.02 s wall 122.26 s
MP2 amplitudes: CPU 0.64 s wall 1.45 s
Running a double precision version
CCSD T amplitudes will be solved using DIIS.
Start Size MaxIter EConv TConv
3 7 100 1.00e-06 1.00e-04
------------------------------------------------------------------------------
Energy (a.u.) Ediff Tdiff Comment
------------------------------------------------------------------------------
-192.77459996
1 -179.83594822 1.29e+01 3.25e+01 Step took 04.31.
2 1.2697265e+04 1.29e+04 5.82e+04
3 2.6704471e+16 2.67e+16 2.81e+11
4 -5.9672497e+12 2.67e+16 2.67e+11 Switched to DIIS steps.
5 2.4276428e+11 6.21e+12 1.27e+10
6 1.3898991e+09 2.41e+11 8.80e+08
7 1.8375754e+08 1.21e+09 5.76e+07
8 3.9242982e+06 1.80e+08 1.54e+07
9 4.1174153e+05 3.51e+06 2.20e+06
10 5.5193096e+18 5.52e+18 5.73e+12
11 2.7372574e+19 2.19e+19 1.10e+12
12 6.0228464e+17 2.68e+19 4.93e+12
13 1.0621670e+17 4.96e+17 1.36e+12
14 9.6868592e+15 9.65e+16 4.47e+11
15 3.3377559e+15 6.35e+15 4.85e+10
16 7.2118731e+16 6.88e+16 3.58e+11
17 3.5806286e+46 3.58e+46 1.02e+32
18 -192.77459996 3.58e+46 1.02e+32
19 -192.77459996 0.00e+00 0.00e+00
------------------------------------------------------------------------------
-192.77459996 CCSD T converged.
End of double precision
WARNING: YOUR (T) CALCULATION MAY RUN OUT OF MEMORY
REDUCE CC_MEMORY OR USE CC_BACKEND=XM IF THIS HAPPENS
----------------------------------------
libpt (c) 2016-2019 Ilya Kaliman
Fast Coupled Cluster Triples Corrections
https://github.com/ilyak/libpt
----------------------------------------
Starting (T) calculation...
Using double precision libpt code
Running restricted (T) code
Using 1 integral batch
(T) calculation completed in 777.93 sec
(T) energy is -0.0333959097
SCF energy = -192.03446983
MP2 energy = -192.77459996
CCSD correlation energy = -0.74013013
CCSD total energy = -192.77459996
CCSD(T) correlation energy = -0.03339591
CCSD(T) total energy = -192.80799587
CCSD T1^2 = 0.0000 T2^2 = 0.2148 Leading amplitudes:
Amplitude Orbitals with energies
Amplitude Orbitals with energies
-0.0522 15 (A) A 15 (A) B -> 18 (A) A 18 (A) B
-0.4886 -0.4886 0.1487 0.1487
0.0522 15 (A) A 15 (A) B -> 18 (A) B 18 (A) A
-0.4886 -0.4886 0.1487 0.1487
0.0522 15 (A) B 15 (A) A -> 18 (A) A 18 (A) B
-0.4886 -0.4886 0.1487 0.1487
-0.0522 15 (A) B 15 (A) A -> 18 (A) B 18 (A) A
-0.4886 -0.4886 0.1487 0.1487
CCSD calculation: CPU 3670.66 s wall 7621.90 s
Total ccman2 time: CPU 3793.29 s wall 7753.64 s
--------------------------------------------------------------
Orbital Energies (a.u.)
--------------------------------------------------------------
Alpha MOs
-- Occupied --
-20.5410 -11.3281 -11.2327 -11.2327 -1.3880 -1.0431 -0.9685 -0.7409
-0.6465 -0.6371 -0.6245 -0.5621 -0.5597 -0.5375 -0.4886 -0.4124
-- Virtual --
0.1270 0.1487 0.1797 0.2045 0.2068 0.2306 0.2447 0.2694
0.3273 0.3438 0.3700 0.3868 0.4109 0.4901 0.5032 0.5109
0.5696 0.5992 0.5994 0.6218 0.6238 0.6303 0.6410 0.6535
0.6859 0.7370 0.7543 0.7908 0.7950 0.8441 0.8896 0.9056
0.9763 1.0405 1.0431 1.0495 1.0679 1.1237 1.1441 1.1641
1.1650 1.1841 1.2176 1.2456 1.2649 1.2814 1.3320 1.3568
1.3734 1.4482 1.4522 1.4915 1.4973 1.5053 1.5187 1.5227
1.5497 1.5895 1.6047 1.6182 1.6784 1.7361 1.7707 1.8316
1.9910 2.0840 2.1223 2.1912 2.4120 2.4162 2.4181 2.4822
2.5278 2.6022 2.6630 2.6812 2.7460 2.7685 2.7918 2.8736
2.9020 2.9184 2.9401 3.0532 3.0671 3.0896 3.0916 3.1074
3.1254 3.1586 3.1835 3.1844 3.2310 3.2752 3.2974 3.3026
3.3077 3.3643 3.3682 3.4139 3.4291 3.4394 3.4923 3.5383
3.5718 3.5969 3.6154 3.6392 3.6581 3.7079 3.7291 3.7581
3.7583 3.8005 3.8094 3.8271 3.8399 3.9712 3.9942 4.0275
4.0422 4.0828 4.0942 4.1133 4.1319 4.1381 4.1673 4.2170
4.2330 4.3068 4.3209 4.3505 4.3608 4.3845 4.4161 4.4481
4.4924 4.5310 4.5330 4.5984 4.6121 4.6294 4.6779 4.7006
4.7134 4.8914 4.8991 4.9536 5.1147 5.1346 5.1671 5.1816
5.2904 5.4037 5.4205 5.4411 5.4604 5.4730 5.4969 5.5122
5.5130 5.5999 5.6108 5.6283 5.6334 5.6689 5.7022 5.7459
5.7705 5.9240 6.0527 6.1837 6.2090 6.2144 6.2505 6.2806
6.7566 6.7709 6.9219 6.9650 7.1751 7.3771 7.5486 7.5748
9.4070 13.7784 14.1467 14.2328
--------------------------------------------------------------
Ground-State Mulliken Net Atomic Charges
Atom Charge (a.u.)
----------------------------------------
1 C 0.292977
2 O -0.350614
3 C -0.291884
4 C -0.291788
5 H 0.127830
6 H 0.096346
7 H 0.096469
8 H 0.127820
9 H 0.096477
10 H 0.096368
----------------------------------------
Sum of atomic charges = 0.000000
-----------------------------------------------------------------
Cartesian Multipole Moments
-----------------------------------------------------------------
Charge (ESU x 10^10)
-0.0000
Dipole Moment (Debye)
X -3.0393 Y -1.2210 Z -0.0280
Tot 3.2755
Quadrupole Moments (Debye-Ang)
XX -12.3005 XY -4.3584 YY -29.0933
XZ -0.0022 YZ 0.2339 ZZ -24.0680
Octopole Moments (Debye-Ang^2)
XXX 161.7354 XXY -23.3312 XYY 60.2171
YYY -149.3542 XXZ 0.1939 XYZ -0.0416
YYZ 2.2148 XZZ 64.6704 YZZ -44.9050
ZZZ 1.6836
Hexadecapole Moments (Debye-Ang^3)
XXXX -1121.2178 XXXY 299.4455 XXYY -271.8214
XYYY 362.8377 YYYY -691.4699 XXXZ 13.0905
XXYZ -12.9406 XYYZ -0.5437 YYYZ -22.1880
XXZZ -209.1754 XYZZ 121.8206 YYZZ -121.4931
XZZZ 8.4686 YZZZ -29.6475 ZZZZ -78.8243
-----------------------------------------------------------------
Archival summary:
1\1\n19\SP\ProcedureUnspecified\BasisUnspecified\136\morgunov\FriAug1217:24:532022FriAug1217:24:532022\0\\#,ProcedureUnspecified,BasisUnspecified,\\0,1\C\O,1,1.20562\C,1,1.50683,2,121.667\H,3,1.08562,1,110.025,2,0.186191,0\H,3,1.09072,1,110.149,2,121.365,0\H,3,1.09077,1,110.147,2,-120.958,0\C,1,1.50684,2,121.664,3,179.858,0\H,7,1.0856,1,110.032,2,-0.222193,0\H,7,1.09069,1,110.136,2,-121.412,0\H,7,1.09073,1,110.102,2,120.932,0\\HF=-192.03447\\@
Total job time: 7834.65s(wall), 3873.76s(cpu)
Fri Aug 12 17:24:53 2022
*************************************************************
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* Thank you very much for using Q-Chem. Have a nice day. *
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