Optimization is not running

Questions
#1

Dear all.

I am trying to run an optimization of methane at the RI-MP2/def2-TZVP (aux=rimp2-def2-tzvp) level of theory. The SCF cycle converged, but it did not performed any optimization steps. Please, can anyone assist me?

The output file is shown below:

Please cite Q-Chem as follows:
Y. Shao et al., Mol. Phys. 113, 184-215 (2015)
DOI: 10.1080/00268976.2014.952696

Q-Chem 5.2.2 for Intel X86 EM64T Linux

Parts of Q-Chem use Armadillo 8.300.2 (Tropical Shenanigans).
http://arma.sourceforge.net/

Q-Chem begins on Mon Jul 10 08:53:03 2023

Host:
0

Nov2519 |scratch|qcdevops|jenkins|workspace|build_RNUM 7080
Processing $rem in /share/apps/q-chem/5.2.2/config/preferences:
MEM_TOTAL 64768
NAlpha2: 10
NElect 10
Mult 1
Core orbitals will be frozen

Checking the input file for inconsistencies… …done.

User input:

$comment
Optimize CH4
$end

$molecule
0 1
6 -0.678803419 0.000000000 0.242564103
1 -0.148369473 -0.951333822 0.318754133
1 0.037744266 0.821859802 0.300070751
1 -1.395351104 0.083844265 1.062155883
1 -1.209237364 0.045629756 -0.710724357
$end

$rem
JOBTYPE OPT
THRESH 12
method RIMP2
BASIS def2-TZVP
AUX_BASIS gen
MEM_TOTAL 400000
CC_MEMORY 200000
MEM_STATIC 5012
$end

$aux_basis
H 0
S 1 1.00
9.33521609 .64609379
S 1 1.00
1.86110704 1.37005241
S 1 1.00
.59512466 1.0000000
S 1 1.00
.26448099 1.0000000
P 2 1.00
2.45249821 .13284956
1.35403830 1.45276215
P 1 1.00
.59522394 1.0000000
D 2 1.00
1.58163766 1.49367397
.62743960 -.01070690

C 0
S 1 1.00
281.47693316 .48911748
S 1 1.00
59.86260691 1.52506644
S 1 1.00
23.28284492 .53278071
S 1 1.00
9.43365439 1.0000000
S 1 1.00
3.31157947 1.0000000
S 1 1.00
1.07438579 1.0000000
S 1 1.00
.40591700 1.0000000
S 1 1.00
.20682782 1.0000000
P 1 1.00
24.79432276 1.27505829
P 1 1.00
6.37908678 1.30659648
P 1 1.00
2.73619827 1.0000000
P 1 1.00
1.13180785 1.0000000
P 1 1.00
.49171280 1.0000000
P 1 1.00
.23760591 1.0000000
D 2 1.00
9.06768796 .47011119
3.41167689 1.34112442
D 1 1.00
1.41501615 1.0000000
D 1 1.00
.58793486 1.0000000
D 1 1.00
.25753087 1.0000000
F 1 1.00
2.38701735 .79093613
F 1 1.00
1.16067992 1.39179984
F 1 1.00
.55289817 .10532469
G 1 1.00
1.22884707 1.0000000

$end

Standard Nuclear Orientation (Angstroms)
I Atom X Y Z

1      C       0.0000000001     0.0000000002    -0.0000000001
2      H      -0.6303969999     0.6303970001     0.6303969999
3      H       0.6303969999    -0.6303970001     0.6303970004
4      H       0.6303969999     0.6303969988    -0.6303970007
5      H      -0.6303970003    -0.6303970001    -0.6303969992

Molecular Point Group Td NOp = 24
Largest Abelian Subgroup D2 NOp = 4
Nuclear Repulsion Energy = 13.41226070 hartrees
There are 5 alpha and 5 beta electrons
Requested basis set is def2-TZVP
There are 27 shells and 55 basis functions

Total QAlloc Memory Limit 400000 MB
Mega-Array Size 4900 MB
MEM_STATIC part 5012 MB
Requested basis set is non-standard
There are 50 shells and 136 basis functions
A cutoff of 1.0D-12 yielded 378 shell pairs
There are 1602 function pairs ( 1926 Cartesian)
Smallest overlap matrix eigenvalue = 1.46E-03

Scale SEOQF with 1.000000e+00/1.000000e+00/1.000000e+00

Standard Electronic Orientation quadrupole field applied
Guess from superposition of atomic densities
Warning: Energy on first SCF cycle will be non-variational
SAD guess density has 10.000000 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     -40.2328497124      6.64e-02  
2     -40.2008086635      5.09e-03  
3     -40.2117141018      1.47e-03  
4     -40.2127426262      4.88e-04  
5     -40.2128781228      6.55e-05  
6     -40.2128819667      6.33e-06  
7     -40.2128820068      5.63e-07  
8     -40.2128820071      3.87e-08  
9     -40.2128820071      3.39e-09  Convergence criterion met

SCF time: CPU 0.47s wall 1.00s
SCF energy in the final basis set = -40.2128820071
Total energy in the final basis set = -40.2128820071

Generalized many-body perturbation theory program
by Joonho Lee, Fazle Rob, Xintian Feng, Evgeny Epifanovsky

#2

There is an error in your input, the output you should receive is as follows:

214  Total QAlloc Memory Limit 400000 MB                                            
215  Mega-Array Size      4900 MB                                                   
216  MEM_STATIC part      5012 MB                                                   
217  Requested basis set is non-standard                                            
218                                                                                 
219  Unexpected End of File Found !!!                                               
220  Line found:  The input format expected here should be:                         
221   <character>   <integer>   <real optional>                                     
222   Or  ****                                                                      
223                                                                                 
224  Q-Chem fatal error occurred in module forms1/AtomicBasis.C, line 1019:         
225                                                                                 
226   Check this line of input !!                                                   
227                                                                                 
228                                                                                 
229  Please submit a crash report at q-chem.com/reporter

This is due incorrect formatting in $aux_basis.

See Example 4.24 in the manual.

But the correction needed for yours is as follows:

$aux_basis
****
H 0
S 1 1.00
9.33521609 .64609379
S 1 1.00
1.86110704 1.37005241
S 1 1.00
.59512466 1.0000000
S 1 1.00
.26448099 1.0000000
P 2 1.00
2.45249821 .13284956
1.35403830 1.45276215
P 1 1.00
.59522394 1.0000000
D 2 1.00
1.58163766 1.49367397
.62743960 -.01070690
****
C 0
S 1 1.00
281.47693316 .48911748
S 1 1.00
59.86260691 1.52506644
S 1 1.00
23.28284492 .53278071
S 1 1.00
9.43365439 1.0000000
S 1 1.00
3.31157947 1.0000000
S 1 1.00
1.07438579 1.0000000
S 1 1.00
.40591700 1.0000000
S 1 1.00
.20682782 1.0000000
P 1 1.00
24.79432276 1.27505829
P 1 1.00
6.37908678 1.30659648
P 1 1.00
2.73619827 1.0000000
P 1 1.00
1.13180785 1.0000000
P 1 1.00
.49171280 1.0000000
P 1 1.00
.23760591 1.0000000
D 2 1.00
9.06768796 .47011119
3.41167689 1.34112442
D 1 1.00
1.41501615 1.0000000
D 1 1.00
.58793486 1.0000000
D 1 1.00
.25753087 1.0000000
F 1 1.00
2.38701735 .79093613
F 1 1.00
1.16067992 1.39179984
F 1 1.00
.55289817 .10532469
G 1 1.00
1.22884707 1.0000000
****
$end
#3

This GUI gobbles up the asterisks unless you use the preformatted text button (looks like </> ), so I’m not sure that is the problem…

CC_MEMORY is not actually required for this job. Not sure if that is the problem.

#4

I don’t think CC_MEMORY is required as well, but the issue is the $aux_basis, I was able to get the job to successfully complete with the **** added.

#5

Dear all
I really appreciated your time! Thank you very much.
I tried this new input file, including the **** and remove the CC_MEMORY, but the calculation still does not performed the optimization. Am I doing something wrong, did I include the corrections correctly?

User input:
$comment
Optimize CH4
$end

$molecule
0 1
6 -0.678803419 0.000000000 0.242564103
1 -0.148369473 -0.951333822 0.318754133
1 0.037744266 0.821859802 0.300070751
1 -1.395351104 0.083844265 1.062155883
1 -1.209237364 0.045629756 -0.710724357
$end
$rem
JOBTYPE OPT
THRESH 12
method RIMP2
BASIS def2-TZVP
AUX_BASIS gen
MEM_TOTAL 400000
MEM_STATIC 5012
$end

$aux_basis
*** (I include the asterisks here)
H 0
S 1 1.00
9.33521609 .64609379
S 1 1.00
1.86110704 1.37005241
S 1 1.00
.59512466 1.0000000
S 1 1.00
.26448099 1.0000000
P 2 1.00
2.45249821 .13284956
1.35403830 1.45276215
P 1 1.00
.59522394 1.0000000
D 2 1.00
1.58163766 1.49367397
.62743960 -.01070690
**** (I include the asterisks here)
C 0
S 1 1.00
281.47693316 .48911748
S 1 1.00
59.86260691 1.52506644
S 1 1.00
23.28284492 .53278071
S 1 1.00
9.43365439 1.0000000
S 1 1.00
3.31157947 1.0000000
S 1 1.00
1.07438579 1.0000000
S 1 1.00
.40591700 1.0000000
S 1 1.00
.20682782 1.0000000
P 1 1.00
24.79432276 1.27505829
P 1 1.00
6.37908678 1.30659648
P 1 1.00
2.73619827 1.0000000
P 1 1.00
1.13180785 1.0000000
P 1 1.00
.49171280 1.0000000
P 1 1.00
.23760591 1.0000000
D 2 1.00
9.06768796 .47011119
3.41167689 1.34112442
D 1 1.00
1.41501615 1.0000000
D 1 1.00
.58793486 1.0000000
D 1 1.00
.25753087 1.0000000
F 1 1.00
2.38701735 .79093613
F 1 1.00
1.16067992 1.39179984
F 1 1.00
.55289817 .10532469
G 1 1.00
1.22884707 1.0000000
**** (I include the asterisks here)
$end

My output ends like this, it only performed a single SCF cycle, with no optimization steps:

Cycle Energy DIIS error
1 -40.2328497124 6.64e-02
2 -40.2008086635 5.09e-03
3 -40.2117141018 1.47e-03
4 -40.2127426262 4.88e-04
5 -40.2128781228 6.55e-05
6 -40.2128819667 6.33e-06
7 -40.2128820068 5.63e-07
8 -40.2128820071 3.87e-08
9 -40.2128820071 3.39e-09 Convergence criterion met
SCF time: CPU 0.48s wall 0.00s
SCF energy in the final basis set = -40.2128820071
Total energy in the final basis set = -40.2128820071

Generalized many-body perturbation theory program
by Joonho Lee, Fazle Rob, Xintian Feng, Evgeny Epifanovsky

#6

I am able to get this job running with 18 threads, I have the input below that does work for me with Q-Chem 5.2.2.

I think one issue might be the MEM_TOTAL 400000, this is 400 GB which is ALOT for this very simple job (takes about 60 secs CPU). Also if the computer you are running this job one doesn’t have that amount of memory it might be causing the issue.

If you are still experiencing issues please contact support@q-chem.com for additional assistance.

$comment
Optimize CH4
$end

$molecule
0 1
6 -0.678803419 0.000000000 0.242564103
1 -0.148369473 -0.951333822 0.318754133
1 0.037744266 0.821859802 0.300070751
1 -1.395351104 0.083844265 1.062155883
1 -1.209237364 0.045629756 -0.710724357
$end

$rem
JOBTYPE OPT
THRESH 12
method RIMP2
BASIS def2-TZVP
AUX_BASIS gen
MEM_TOTAL 400000
CC_MEMORY 200000
MEM_STATIC 5012
$end

$aux_basis
****
H 0
S 1 1.00
9.33521609 .64609379
S 1 1.00
1.86110704 1.37005241
S 1 1.00
.59512466 1.0000000
S 1 1.00
.26448099 1.0000000
P 2 1.00
2.45249821 .13284956
1.35403830 1.45276215
P 1 1.00
.59522394 1.0000000
D 2 1.00
1.58163766 1.49367397
.62743960 -.01070690
****
C 0
S 1 1.00
281.47693316 .48911748
S 1 1.00
59.86260691 1.52506644
S 1 1.00
23.28284492 .53278071
S 1 1.00
9.43365439 1.0000000
S 1 1.00
3.31157947 1.0000000
S 1 1.00
1.07438579 1.0000000
S 1 1.00
.40591700 1.0000000
S 1 1.00
.20682782 1.0000000
P 1 1.00
24.79432276 1.27505829
P 1 1.00
6.37908678 1.30659648
P 1 1.00
2.73619827 1.0000000
P 1 1.00
1.13180785 1.0000000
P 1 1.00
.49171280 1.0000000
P 1 1.00
.23760591 1.0000000
D 2 1.00
9.06768796 .47011119
3.41167689 1.34112442
D 1 1.00
1.41501615 1.0000000
D 1 1.00
.58793486 1.0000000
D 1 1.00
.25753087 1.0000000
F 1 1.00
2.38701735 .79093613
F 1 1.00
1.16067992 1.39179984
F 1 1.00
.55289817 .10532469
G 1 1.00
1.22884707 1.0000000
****
$end
#7

Dear all,

Thank you for your help. I was able to run successfully the RI-MP2 calculation. It worked just by removing the memory request.