Dear All -

I am trying to optimize a big structure (105 atoms with a Zn ion in the middle). I am using a mixed basis/ecp set for the system where an external basis set (aug-cc-pVDZ-PP) for the Zn ion. Here are the relevant parts in my input files:

-------------- qchem.inp -------------------
$comment
Comments regarding the system
$end

$molecule
-2 1
.
.
.
(all the coordinates)
.
.
.
$end

$rem
Basis general
ECP general
Exchange HF
Jobtype OPT Optimize the structure
GEOM_OPT_MAX_CYCLES 1000
max_SCF_CYCLEs 200
MEM_STATIC 500
mem_total 20000
IANLTY 0
$end

$opt
CONSTRAINT
bend 14 105 44 109.5
bend 14 105 66 109.5
bend 14 105 96 109.5
bend 44 105 66 109.5
bend 66 105 96 109.5
bend 96 105 44 109.5
tors 2 5 7 9 170.92
tors 5 7 9 15 -76.80
tors 7 9 15 17 128.14
tors 9 15 17 19 -177.45
tors 15 17 19 25 -70.31
tors 17 19 25 27 -41.25
tors 19 25 27 29 -176.95
tors 25 27 29 35 -82.32
tors 27 29 35 37 -64.78
tors 29 35 37 39 -175.92
tors 35 37 39 45 -78.70
tors 37 39 45 47 -14.56
tors 39 45 47 49 168.60
tors 54 57 59 61 177.70
tors 57 59 61 67 -82.98
tors 59 61 67 69 170.01
tors 61 67 69 71 -175.26
tors 67 69 71 77 -48.87
tors 69 71 77 79 -58.06
tors 71 77 79 81 178.58
tors 77 79 81 87 -50.38
tors 79 81 87 89 -40.24
tors 81 87 89 91 178.94
tors 87 89 91 97 -73.38
tors 89 91 97 99 -30.23
tors 91 97 99 101 179.41
ENDCONSTRAINT
$end

$basis
N
6-31G*
****
C
6-31G*
****
S
6-31G*
****
O
6-31G*
****
H
6-31G*
****
Zn
S 7 1.00
629.1260000 0.0005590
62.9635000 -0.0096800
39.5791000 0.0623540
11.9173000 -0.4148790
2.5082400 0.7544660
1.0301900 0.4589960
0.1540020 0.0116640
S 7 1.00
629.1260000 -0.0001210
62.9635000 0.0014890
39.5791000 -0.0127370
11.9173000 0.0972460
2.5082400 -0.2199170
1.0301900 -0.2364740
0.1540020 0.5812910
S 7 1.00
629.1260000 0.0004210
62.9635000 -0.0051090
39.5791000 0.0414470
11.9173000 -0.3416430
2.5082400 1.4386170
1.0301900 -0.9824290
0.1540020 -1.1876310
S 1 1.00
0.0527950 1.0000000
S 1 1.00
0.0181000 1.0000000
P 6 1.00
92.9034000 0.0024880
19.7452000 -0.0791360
4.5507300 0.3880590
2.0019000 0.5093540
0.8438790 0.2245750
0.2033810 0.0126800
P 6 1.00
92.9034000 -0.0004030
19.7452000 0.0154470
4.5507300 -0.0843250
2.0019000 -0.1364890
0.8438790 0.0008020
0.2033810 0.5157920
P 6 1.00
92.9034000 -0.0005300
19.7452000 0.0247430
4.5507300 -0.1424780
2.0019000 -0.2340320
0.8438790 0.0921870
0.2033810 0.8377700
P 1 1.00
0.0595720 1.0000000
P 1 1.00
0.0174000 1.0000000
D 5 1.00
71.2766000 0.0158950
22.7604000 0.0924540
8.3236900 0.2594720
3.1687500 0.4033140
1.1470300 0.3878340
D 5 1.00
71.2766000 -0.0225160
22.7604000 -0.1333030
8.3236900 -0.3932530
3.1687500 -0.3512140
1.1470300 0.4061710
D 1 1.00
0.3666430 1.0000000
D 1 1.00
0.1172000 1.0000000
F 1 1.00
3.2168000 1.0000000
F 1 1.00
1.0870000 1.0000000
****
$end

$ecp
Zn
ZN-ECP 4 10
g-ul potential
1
2 1.0000000 0.0000000
s-ul potential
2
2 34.1740010 399.9863990
2 14.4563710 85.4897500
p-ul potential
4
2 39.8886830 92.3810770
2 39.6550170 184.7711760
2 15.2905460 23.0025410
2 14.9035240 46.0574270
d-ul potential
4
2 43.7082960 -13.6907340
2 43.6985360 -20.5439800
2 15.1507180 -1.3161540
2 15.2824410 -1.8387150
f-ul potential
2
2 8.1600140 -0.3703600
2 12.2284220 -1.0629430
****
$end
----------------------------------------------------------------

I use 6x12 cores for the optimization process. Initially, qchem works fine; takes the data/variables and minimizes the energy. Right after that, I am getting the following error message:

====== qchem.out ======
.
.
.
25 -4274.6505202080 4.00E-08
26 -4274.6505202083 1.59E-08
27 -4274.6505202058 7.51E-09 Convergence criterion met
---------------------------------------
SCF time: CPU 209.66 s wall 878.29 s
No wavefunction analysis requested
Calculating analytic gradient of the SCF energy
rm_l_63_23113: (957.660156) net_send: could not write to fd=5, errno = 32

Q-Chem fatal error occurred in module Shells.C, line 46:

In ~Shells: s1Ints != 0.
==============================

Something happens right after the minimization when calculating the analytical gradient of SCF energy. I initially thought that it is because of memory, but changing the mem_static or mem_total did not do anything good. Interestingly, however, if I used the build in lanl2dz basis set for Zn, optimization finishes.

I will appreciate if anyone can suggest me anything in order to finish this optimization. I am using a lot of constraints in the system, so the minimization should not take too many steps, but getting the above error message makes me wonder what I am doing wrong. Thanks in advance.

Best regards,

Ilyas

Can you provide the coordinates?

Hello
I have encountered a very similar behaviour to this example.
With
User input:
--------------------------------------------------------------
$molecule
2 1
Pd -1.59582600 0.00000200 -0.06377500
O 0.00007500 -1.36359000 -0.15199000
N -4.27101500 1.18374000 -0.60396000
N -3.15467500 -2.53516000 0.63242200
C -3.07091200 1.34583000 0.00658300
C -4.39297700 3.11824000 0.41099800
H -4.65487700 4.07898900 0.83133100
C -4.59545800 0.00008400 -1.37487300
H -5.66506400 0.00009900 -1.59916000
H -4.03354900 0.00022500 -2.31563000
C -3.07092000 -1.34585600 0.00638500
C -2.12657500 -3.12523600 1.48115800
H -1.95360000 -4.16012500 1.17285100
H -2.45002200 -3.10663300 2.52537700
H -1.20772500 -2.54744600 1.35818900
N -3.15449700 2.53524200 0.63243000
C -4.39318100 -3.11809000 0.41096600
H -4.65519500 -4.07876600 0.83139800
C -5.10080400 -2.26847800 -0.36762700
H -6.09868200 -2.33919700 -0.77665400
N -4.27097200 -1.18374100 -0.60426600
C -2.12648700 3.12514800 1.48141100
H -2.44976600 3.10567500 2.52567100
H -1.95405300 4.16032500 1.17380200
H -1.20743100 2.54780100 1.35791800
C 0.00015100 -2.18322400 -1.30305300
H 0.00006700 -1.60056600 -2.23797100
H -0.88850700 -2.83268400 -1.31133000
H 0.88895600 -2.83248400 -1.31142300
C -5.10070000 2.26862100 -0.36750700
H -6.09861700 2.33934800 -0.77643500
Pd 1.59581300 0.00003200 -0.06374500
O -0.00007900 1.36360500 -0.15204400
N 4.27099500 -1.18382000 -0.60390700
N 3.15471200 2.53527800 0.63231300
C 3.07086200 -1.34587100 0.00658000
C 4.39284200 -3.11834600 0.41101100
H 4.65466900 -4.07913000 0.83131200
C 4.59558000 -0.00014100 -1.37471900
H 5.66522300 -0.00018700 -1.59883700
H 4.03382600 -0.00019800 -2.31557100
C 3.07093900 1.34590700 0.00639900
C 2.12651400 3.12574400 1.48065900
H 1.95262200 4.16008700 1.17102200
H 2.45047500 3.10881300 2.52474900
H 1.20805200 2.54708900 1.35889400
N 3.15435700 -2.53533300 0.63236100
C 4.39329800 3.11808100 0.41098400
H 4.65534300 4.07875400 0.83140300
C 5.10095300 2.26833400 -0.36743700
H 6.09892900 2.33888600 -0.77625200
N 4.27106700 1.18364300 -0.60406900
C 2.12625400 -3.12535400 1.48115100
H 2.44982300 -3.10681500 2.52533300
H 1.95319700 -4.16021800 1.17281500
H 1.20746000 -2.54746500 1.35829600
C 0.00005000 2.18317100 -1.30312700
H 0.00002300 1.60048300 -2.23803200
H 0.88883600 2.83245300 -1.31148500
H -0.88860200 2.83265500 -1.31155300
C 5.10064400 -2.26871900 -0.36741400
H 6.09858100 -2.33945400 -0.77629200
$end
$rem
JOBTYPE OPT
EXCHANGE M11L
MAX_SCF_CYCLES 250
ECP GEN
BASIS GEN
$end
$BASIS
C
6-31G*
****
H
6-31G(d,p)
****
N
6-31G*
****
O
6-31G*
****
Pd 0
S 1 1.00
2.7870000 1.0000000
S 1 1.00
1.9650000 1.0000000
S 1 1.00
0.6243000 1.0000000
S 1 1.00
0.1496000 1.0000000
S 1 1.00
0.0436000 1.0000000
P 1 1.00
5.9990000 1.0000000
P 1 1.00
1.4430000 1.0000000
P 1 1.00
0.5264000 1.0000000
P 1 1.00
0.0899000 1.0000000
P 1 1.00
0.0262000 1.0000000
D 2 1.00
6.0910000 0.0376146
1.7190000 0.5200479
D 1 1.00
0.6056000 1.0000000
D 1 1.00
0.1883000 1.0000000
F 1 1.00
1.4720000 1.0000000
****
$end
$ECP
PD
PD-ECP 3 28
f potential
5
0 598.3336444 -0.0563177
1 162.4298290 -20.1288036
2 51.5714771 -105.8197923
2 16.4888260 -42.5733345
2 5.8287656 -3.6165086
s-f potential
5
0 73.3806304 3.0003651
1 14.7550438 32.4350093
2 17.8350204 459.0830383
2 12.7111477 -868.0629029
2 9.3292063 514.4726098
p-f potential
5
0 55.6689877 4.9593099
1 64.2337771 21.1711029
2 17.6254952 605.0560092
2 11.9058155 -726.9641846
2 8.5100832 396.3274883
d-f potential
5
0 49.9994728 3.0508745
1 39.7477547 22.2506580
2 11.4321366 674.8357698
2 9.1790080 -1040.8554048
2 7.5624429 505.9375147
****
$end
The calculation ends at
Calculating analytic gradient of the SCF energy
rm_l_1_11805: (1474.30468 net_send: could not write to fd=5, errno = 32
rm_l_2_11848: (1474.093750) net_send: could not write to fd=5, errno = 32

Q-Chem fatal error occurred in module /home/scratch/svnadmin/qc40c/qchem/forms1/Shells.C, line 46:

In ~Shells: s1Ints != 0.

p0_11761: p4_error: interrupt SIGx: 6

Whilst when the Pd basis and ECP are replaced by LANL2DZ the optimization proceeds.

Is there any information about this

Cheers
Peter

Q-Chem does not yet support analytical gradient with f basis functions and ECP. Working on that...