Problem with MECP for the ground states

Questions
#1

I am attempting to calculate MECP for a molecule, but every time one of the states (MECP STATE) is set to ground stat (j=0), the calculation hangs without error. Is there a keyword to use for the ground stat that was left out?
I calculated this using spin flip methods, but the problem remains. I have included the input and end of the output below for S0/T1 MECP.

RAM AND CPU:
NCPUs Requested: 15 NCPUs Used: 15
CPU Time Used: 05:43:18
Memory Requested: 8.0GB Memory Used: 1.55GB
Walltime requested: 15:00:00 Walltime Used: 00:25:03
JobFS requested: 10.0GB JobFS used: 204.05MB

INPUT:
$molecule
0 1
O 1.0709671 0.9397235 0.0028675
C -0.0123565 0.1494701 -0.0075998
C -1.2839944 0.8412414 0.0078677
C 0.0336163 -1.2377508 -0.0333228
C -2.4752747 0.0470585 0.0029710
C -1.1421820 -1.9718690 -0.0392955
H 0.9870294 -1.7509705 -0.0493534
C -2.3837705 -1.3170388 -0.0193843
H -3.4356652 0.5430282 0.0149695
H -1.1015615 -3.0546592 -0.0598990
C 2.3453926 0.3768576 0.0054432
C 2.9358285 0.0432302 1.2154424
C 3.0142986 0.2389530 -1.2016932
C 4.2370921 -0.4487077 1.2099553
H 2.3843314 0.1745684 2.1406109
C 4.3153304 -0.2530926 -1.1923260
H 2.5212169 0.5206471 -2.1260550
C 4.9264622 -0.5976001 0.0099462
H 4.7128608 -0.7116043 2.1493987
H 4.8518518 -0.3637614 -2.1292738
H 5.9426285 -0.9785813 0.0122644
Cl -3.8407765 -2.2830496 -0.0253388
N -1.2259741 2.1653645 0.0251376
N -2.6759387 2.7568124 0.0318009
N -2.8417345 3.8915464 0.0441541
$end

$rem
JOBTYPE opt
MECP_OPT true
MECP_METHODS branching_plane
MECP_PROJ_HESS true
GEOM_OPT_COORDS 0
METHOD cam-b3lyp
BASIS GEN
PURECART 11
CIS_N_ROOTS 4
CIS_TRIPLETS false
CIS_SINGLETS true
MECP_STATE1 [0,0]
MECP_STATE2 [0,1]
SOLVENT_METHOD smd
SET_ITER 500
MAX_SCF_CYCLES 500
$end

$smx
solvent thf
$end

$basis
H 0
S 3 1.00
34.0613410 0.60251978D-02
5.1235746 0.45021094D-01
1.1646626 0.20189726
S 1 1.00
0.32723041 1.0000000
S 1 1.00
0.10307241 1.0000000
P 1 1.00
0.8000000 1.0000000

C 0
S 6 1.00
13575.3496820 0.22245814352D-03
2035.2333680 0.17232738252D-02
463.22562359 0.89255715314D-02
131.20019598 0.35727984502D-01
42.853015891 0.11076259931
15.584185766 0.24295627626
S 2 1.00
6.2067138508 0.41440263448
2.5764896527 0.23744968655
S 1 1.00
0.57696339419 1.0000000
S 1 1.00
0.22972831358 1.0000000
S 1 1.00
0.95164440028D-01 1.0000000
P 4 1.00
34.697232244 0.53333657805D-02
7.9582622826 0.35864109092D-01
2.3780826883 0.14215873329
0.81433208183 0.34270471845
P 1 1.00
0.28887547253 .46445822433
P 1 1.00
0.10056823671 .24955789874
D 1 1.00
1.09700000 1.0000000
D 1 1.00
0.31800000 1.0000000
F 1 1.00
0.76100000 1.0000000

N 0
S 6 1.00
19730.8006470 0.21887984991D-03
2957.8958745 0.16960708803D-02
673.22133595 0.87954603538D-02
190.68249494 0.35359382605D-01
62.295441898 0.11095789217
22.654161182 0.24982972552
S 2 1.00
8.9791477428 0.40623896148
3.6863002370 0.24338217176
S 1 1.00
0.84660076805 1.0000000
S 1 1.00
0.33647133771 1.0000000
S 1 1.00
0.13647653675 1.0000000
P 4 1.00
49.200380510 0.55552416751D-02
11.346790537 0.38052379723D-01
3.4273972411 0.14953671029
1.1785525134 0.34949305230
P 1 1.00
0.41642204972 .45843153697
P 1 1.00
0.14260826011 .24428771672
D 1 1.00
1.65400000 1.0000000
D 1 1.00
0.46900000 1.0000000
F 1 1.00
1.09300000 1.0000000

O 0
S 6 1.00
27032.3826310 0.21726302465D-03
4052.3871392 0.16838662199D-02
922.32722710 0.87395616265D-02
261.24070989 0.35239968808D-01
85.354641351 0.11153519115
31.035035245 0.25588953961
S 2 1.00
12.260860728 0.39768730901
4.9987076005 0.24627849430
S 1 1.00
1.1703108158 1.0000000
S 1 1.00
0.46474740994 1.0000000
S 1 1.00
0.18504536357 1.0000000
P 4 1.00
63.274954801 0.60685103418D-02
14.627049379 0.41912575824D-01
4.4501223456 0.16153841088
1.5275799647 0.35706951311
P 1 1.00
0.52935117943 .44794207502
P 1 1.00
0.17478421270 .24446069663
D 1 1.00
2.31400000 1.0000000
D 1 1.00
0.64500000 1.0000000
F 1 1.00
1.42800000 1.0000000

Cl 0
S 7 1.00
69507.9909450 0.54314897497D-03
10426.1568800 0.41990463961D-02
2373.2334061 0.21592141679D-01
671.56420071 0.84598850094D-01
218.41999790 0.24757249724
77.572249714 0.47016930228
28.888815277 0.37436370716
S 3 1.00
127.10527185 0.25182166603D-01
39.339582961 0.10786112456
7.6740679989 -0.27408821574
S 2 1.00
3.8745627630 1.3213875014
1.8385832573 0.68636955368
S 1 1.00
0.50229057542 1.0000000
S 1 1.00
0.17962723420 1.0000000
P 5 1.00
666.50423284 0.23632663836D-02
157.64241690 0.18879300374D-01
50.262520978 0.87206341273D-01
18.536078105 0.25285612970
7.2940532777 0.43507154820
P 1 1.00
2.9433248995 .35026513165
P 1 1.00
1.0404970818 1.0000000
P 1 1.00
0.38456415080 1.0000000
P 1 1.00
0.13069642732 1.0000000
D 2 1.00
4.61000000 0.20000000
1.01100000 1.00000000
D 1 1.00
0.339000000 1.0000000
F 1 1.00
0.706000000 1.0000000

$end

OUTPUT:

     TDDFT/TDA Excitation Energies

Excited state 1: excitation energy (eV) = 0.0940
Total energy for state 1: -1161.55361208 au
Multiplicity: Singlet
Trans. Mom.: 0.0003 X -0.0095 Y 0.0489 Z
Strength : 0.0000057197
D( 62) → V( 1) amplitude = -0.2190
D( 63) → V( 1) amplitude = 0.9477

Excited state 2: excitation energy (eV) = 2.3464
Total energy for state 2: -1161.47083642 au
Multiplicity: Singlet
Trans. Mom.: -0.0082 X -0.0042 Y 0.0120 Z
Strength : 0.0000131850
D( 62) → V( 1) amplitude = 0.9365
D( 63) → V( 1) amplitude = 0.2555

Excited state 3: excitation energy (eV) = 3.0610
Total energy for state 3: -1161.44457552 au
Multiplicity: Singlet
Trans. Mom.: 0.1084 X -1.0901 Y -0.0168 Z
Strength : 0.0900223368
D( 55) → V( 1) amplitude = 0.2567
D( 56) → V( 1) amplitude = -0.3232
D( 61) → V( 1) amplitude = 0.2134
D( 63) → V( 2) amplitude = -0.8310

Excited state 4: excitation energy (eV) = 3.5306
Total energy for state 4: -1161.42731746 au
Multiplicity: Singlet
Trans. Mom.: -0.5343 X 0.6248 Y 0.0061 Z
Strength : 0.0584609984
D( 61) → V( 1) amplitude = 0.9505
D( 63) → V( 2) amplitude = 0.2458

Calculating Relaxed Density

Iter Rts Conv Rts Left Ttl Dev Max Dev

1 0 4 0.001027 0.000345
2 0 4 0.000505 0.000169
3 0 4 0.000150 0.000049
4 0 4 0.000062 0.000021
5 0 4 0.000021 0.000008
6 0 4 0.000010 0.000004
7 2 2 0.000006 0.000003
8 2 2 0.000005 0.000003
9 2 2 0.000002 0.000001
10 4 0 0.000000 0.000000 Roots Converged

SETman timing summary (seconds)
CPU time 13671.47s
System time 0.00s
Wall time 1019.15s

                Orbital Energies (a.u.)

Alpha MOs
– Occupied –
******** -19.2431 -14.5759 -14.5439 -14.4626 -10.3231 -10.3137 -10.3064
-10.3061 -10.2598 -10.2548 -10.2547 -10.2546 -10.2536 -10.2534 -10.2504
-10.2483 -9.5298 -7.2924 -7.2838 -7.2834 -1.2360 -1.1771 -1.0278
-0.9684 -0.9492 -0.9071 -0.8467 -0.8380 -0.8262 -0.7968 -0.7392
-0.7112 -0.6958 -0.6585 -0.6524 -0.6289 -0.6039 -0.5838 -0.5790
-0.5723 -0.5527 -0.5495 -0.5301 -0.5161 -0.5122 -0.5004 -0.4931
-0.4882 -0.4617 -0.4505 -0.4478 -0.4364 -0.4247 -0.4174 -0.4097
-0.4050 -0.3792 -0.3701 -0.3215 -0.3103 -0.3012 -0.2484
– Virtual –
-0.1205 -0.0316 0.0231 0.0300 0.0371 0.0527 0.0784 0.0933
0.1108 0.1152 0.1211 0.1242 0.1386 0.1442 0.1552 0.1561
0.1719 0.1766 0.1895 0.1952 0.1980 0.2189 0.2327 0.2338
0.2370 0.2459 0.2563 0.2635 0.2645 0.2685 0.2782 0.2825
0.2832 0.2880 0.2922 0.2961 0.3038 0.3153 0.3210 0.3256
0.3334 0.3390 0.3407 0.3449 0.3548 0.3606 0.3650 0.3725
0.3852 0.3876 0.3909 0.3933 0.4013 0.4063 0.4148 0.4167
0.4179 0.4274 0.4308 0.4319 0.4390 0.4484 0.4569 0.4649
0.4663 0.4679 0.4734 0.4778 0.4839 0.4950 0.5073 0.5171
0.5180 0.5311 0.5328 0.5337 0.5377 0.5449 0.5487 0.5501
0.5549 0.5590 0.5636 0.5663 0.5938 0.6055 0.6123 0.6156
0.6291 0.6334 0.6411 0.6620 0.6696 0.6880 0.6966 0.7018
0.7091 0.7159 0.7311 0.7325 0.7392 0.7509 0.7546 0.7622
0.7646 0.7784 0.7930 0.7959 0.8035 0.8067 0.8104 0.8142
0.8297 0.8379 0.8408 0.8664 0.8690 0.8738 0.8753 0.8885
0.8996 0.9094 0.9226 0.9266 0.9483 0.9509 0.9563 0.9611
0.9837 0.9954 1.0117 1.0218 1.0482 1.0496 1.0621 1.0693
1.0800 1.0988 1.1140 1.1244 1.1298 1.1477 1.1542 1.1650
1.1836 1.1941 1.1981 1.1993 1.2075 1.2179 1.2342 1.2673
1.2698 1.2753 1.2795 1.2861 1.2870 1.2941 1.3106 1.3149
1.3292 1.3364 1.3501 1.3539 1.3617 1.3771 1.3862 1.4192
1.4308 1.4504 1.4559 1.4639 1.4851 1.5008 1.5085 1.5113
1.5168 1.5251 1.5427 1.5503 1.5574 1.5606 1.5686 1.5804
1.5914 1.5966 1.6225 1.6371 1.6470 1.6606 1.6756 1.6802
1.6937 1.6978 1.7016 1.7196 1.7237 1.7421 1.7430 1.7482
1.7566 1.7626 1.7659 1.7775 1.7982 1.7991 1.8134 1.8291
1.8384 1.8491 1.8560 1.8621 1.8722 1.8770 1.8787 1.9147
1.9216 1.9236 1.9427 1.9462 1.9499 1.9751 1.9808 1.9921
2.0013 2.0154 2.0226 2.0540 2.0595 2.0634 2.0668 2.0732
2.1074 2.1242 2.1299 2.1525 2.1574 2.1636 2.1664 2.1689
2.1810 2.1918 2.1973 2.2055 2.2186 2.2242 2.2461 2.2635
2.2683 2.2762 2.2933 2.3019 2.3050 2.3216 2.3226 2.3293
2.3490 2.3628 2.3734 2.3809 2.3923 2.4029 2.4081 2.4338
2.4605 2.5004 2.5079 2.5360 2.5647 2.5734 2.5993 2.6049
2.6165 2.6379 2.6460 2.6525 2.6562 2.6682 2.6724 2.6973
2.7073 2.7119 2.7293 2.7327 2.7345 2.7459 2.7496 2.7516
2.7629 2.7646 2.7922 2.7965 2.8060 2.8241 2.8289 2.8413
2.8441 2.8576 2.8644 2.8660 2.8855 2.8861 2.8972 2.9115
2.9238 2.9276 2.9342 2.9548 2.9555 2.9642 2.9851 2.9917
3.0025 3.0270 3.0406 3.0426 3.0462 3.0559 3.0744 3.0917
3.1114 3.1213 3.1412 3.1437 3.1626 3.1791 3.1799 3.1946
3.1978 3.2093 3.2119 3.2216 3.2327 3.2411 3.2447 3.2537
3.2754 3.2779 3.2807 3.2859 3.2911 3.3185 3.3217 3.3323
3.3372 3.3392 3.3538 3.3610 3.3785 3.3833 3.3992 3.4103
3.4355 3.4381 3.4404 3.4491 3.4534 3.4628 3.4758 3.4927
3.5008 3.5089 3.5111 3.5239 3.5367 3.5376 3.5409 3.5443
3.5656 3.5685 3.5833 3.5924 3.5950 3.6008 3.6178 3.6276
3.6389 3.6410 3.6606 3.6833 3.6947 3.6973 3.7208 3.7463
3.7737 3.7959 3.8009 3.8018 3.8067 3.8410 3.8551 3.8621
3.8859 3.9174 3.9230 3.9496 3.9533 3.9709 4.0047 4.0273
4.0489 4.0530 4.0643 4.0870 4.0924 4.1186 4.1311 4.1399
4.1597 4.1685 4.1980 4.2035 4.2172 4.2404 4.2577 4.2615
4.2700 4.2811 4.2847 4.2993 4.3029 4.3279 4.3342 4.3450
4.3510 4.3605 4.3751 4.3940 4.4244 4.4286 4.4531 4.5003
4.5054 4.5269 4.5367 4.5931 4.6135 4.6477 4.6621 4.6748
4.6916 4.7030 4.7235 4.7354 4.7411 4.7622 4.7684 4.7857
4.7967 4.8031 4.8370 4.8700 4.8996 4.9009 4.9228 4.9445
4.9582 4.9923 4.9962 5.0172 5.0415 5.0813 5.1490 5.1902
5.1940 5.2122 5.2299 5.2444 5.3106 5.3259 5.3381 5.3454
5.3753 5.4579 5.4760 5.4884 5.5371 5.5452 5.6285 5.6535
5.7137 5.7601 5.9310 5.9933 6.0391 6.1289 6.2243 6.2949
6.3655 6.4433 6.5321 6.7165 6.7479 6.7989 6.9645 7.1275
7.3027 7.5482 10.7831 10.8714 11.4103 22.1760 22.2627 22.6339
22.6371 22.7150 22.7520 22.7566 22.8457 22.9128 22.9781 23.2494
23.4386 25.9582 31.4877 32.1427 32.2777 44.5591

      Ground-State Mulliken Net Atomic Charges

 Atom                 Charge (a.u.)

  1 O                    -0.273434
  2 C                     0.178229
  3 C                     0.127859
  4 C                    -0.229230
  5 C                    -0.247741
  6 C                    -0.255732
  7 H                     0.189881
  8 C                     0.117189
  9 H                     0.163734
 10 H                     0.159771
 11 C                     0.187995
 12 C                    -0.201503
 13 C                    -0.203946
 14 C                    -0.147380
 15 H                     0.169218
 16 C                    -0.148163
 17 H                     0.167894
 18 C                    -0.156287
 19 H                     0.164482
 20 H                     0.164165
 21 H                     0.162649
 22 Cl                   -0.120504
 23 N                    -0.201733
 24 N                     0.214697
 25 N                     0.017888

Sum of atomic charges = 0.000000

                Cartesian Multipole Moments

Charge (ESU x 10^10)
             0.0000
Dipole Moment (Debye)
     X       1.6531      Y       0.8991      Z       0.0199
   Tot       1.8819
Quadrupole Moments (Debye-Ang)
    XX     -91.0359     XY     -16.7995     YY    -105.2325
    XZ      -0.4653     YZ      -0.7111     ZZ    -100.0215
Octopole Moments (Debye-Ang^2)
   XXX      37.9860    XXY      21.7839    XYY     -22.5001
   YYY       9.6511    XXZ      -1.5756    XYZ      -3.0637
   YYZ      -0.0578    XZZ      17.4742    YZZ       6.4069
   ZZZ       0.5078
Hexadecapole Moments (Debye-Ang^3)
  XXXX   -4948.2561   XXXY    -267.7986   XXYY   -1204.7550
  XYYY     -35.4778   YYYY   -1748.0834   XXXZ     -15.2587
  XXYZ     -11.2471   XYYZ       1.4691   YYYZ       1.6427
  XXZZ    -880.1766   XYZZ     -13.8502   YYZZ    -365.1772
  XZZZ      -1.5998   YZZZ      -5.0244   ZZZZ    -333.5344

calculating CIS gradients for MECP_OPT
State (1) is the ground state!
Calculating analytic gradient of the SCF energy
Gradient of CDS energy
1 2 3 4 5 6
1 -0.0001456 -0.0003260 -0.0000026 0.0003977 -0.0002477 -0.0000169
2 0.0002895 -0.0000306 -0.0001613 -0.0001664 0.0001224 -0.0004368
3 -0.0000140 0.0000039 -0.0000048 -0.0000075 0.0000056 -0.0000079
7 8 9 10 11 12
1 0.0000682 -0.0003954 0.0000769 -0.0000951 0.0004515 -0.0003264
2 0.0001089 -0.0002027 -0.0001330 -0.0000048 -0.0001215 0.0000698
3 0.0000082 -0.0000002 -0.0000024 0.0000006 0.0000253 0.0002494
13 14 15 16 17 18
1 -0.0003227 0.0001906 -0.0000836 0.0002386 -0.0000875 0.0005093
2 0.0001199 -0.0001158 0.0000327 -0.0000457 0.0000304 -0.0001932
3 -0.0002680 0.0004682 -0.0000477 -0.0004677 0.0000468 0.0000010
19 20 21 22 23 24
1 -0.0000079 -0.0000090 -0.0000172 0.0001747 0.0004748 -0.0002870
2 0.0000044 0.0000019 0.0000064 0.0001115 0.0003428 -0.0002289
3 -0.0000157 0.0000157 -0.0000000 0.0000004 0.0000075 -0.0000034
25
1 -0.0002116
2 0.0006001
3 0.0000066

#2

There seems to be a segfault with this job. I am still trying to look into this job and the reason for it and possible temporary solutions.

#3

So SMD solvent is not supported for excited state gradients, refer to Table 11.2.

#4

Hi Farshad,
I believe what Peter says is correct although I don’t think that is obvious from the manual, I will try to make it more clear for next release. SOLVENT_METHOD = PCM is definitely supported for excited-state gradients, although PCMs in Q-Chem do not contain the nonelectrostatic corrections that are contained in the SMx models. (For a discussion, see this review: 10.1002/wcms.1519.)

Also, I notice that you refer to this job as S0/T1 MECP but the way that it is set up is to look for singlet states even upon changing the solvent model, this job will look for S0/S1 MECP.

#5

Dear Peter and John, Thank you; I followed your advice and used SOLVENT METHOD = PCM, and the problem was solved. As John pointed out, I made a mistake in defining the states, which I corrected.

Just one more question, If I want to calculate S0/T1 MECP in the spin flip method for a singlet molecule with charge=0 (0 1), am I correct in defining triplet state as MECP STATE2=[1,0] according to the high spin reference in spin flip (0 3)? In other words, should I define the first triplet state as the ground state of high spin reference?

Thank you very much

#6

I think that is correct.