Hi , I have searched similar topics which were opened earlier but these answers did not help to me.
My input (I used def2-SVP basis set. The charge is 0 and multiplicity is 1):
$rem
jobtype opt
exchange b3lyp
basis gen
purecart 11
CIS_STATE_DERIV 1
cis_n_roots 10
cis_singlets true
cis_triplets false
state_analysis true
gui 2
max_scf_cycles 500
mem_total 10000
$end
What I got is the following:
CIS energy converged when residual is below 10e- 6
Iter Rts Conv Rts Left Ttl Dev Max Dev
1 0 10 0.002390 0.000527
2 0 10 0.000719 0.000255
3 0 10 0.000243 0.000129 Collapsing Subspace
4 0 10 0.000112 0.000066
5 2 8 0.000068 0.000040 Collapsing Subspace
6 5 5 0.000043 0.000029
7 6 4 0.000033 0.000024
8 8 2 0.000024 0.000018
9 9 1 0.000018 0.000014
10 9 1 0.000013 0.000009 Collapsing Subspace
11 9 1 0.000013 0.000009
12 9 1 0.000013 0.000009
13 9 1 0.000014 0.000010
14 9 1 0.000014 0.000010
15 9 1 0.000011 0.000007
16 9 1 0.000008 0.000004
17 9 1 0.000007 0.000003
18 9 1 0.000006 0.000002
19 10 0 0.000005 0.000001 Roots Converged
Q-Chem fatal error:
Unable to diagonalize A-B.
I have set RPA=0. But it doesn’t work. What should I do to fix this problem?
Thanks!
This is the coordinate:
$molecule
0 1
C 2.47893970 1.76878137 0.05529023
C 1.24788277 1.08542868 0.01974460
C -0.00314249 1.75539977 -0.00128266
C -0.00531774 3.19383591 0.00440011
C 1.23754191 3.88260019 0.03108371
C 2.43184071 3.19910667 0.05431724
H -1.22902673 -0.00918627 -0.00581792
H 1.22806944 -0.00546940 -0.00917271
C -1.25218683 1.08181290 -0.02699979
C -1.25024142 3.87905841 -0.01657285
H 1.23332229 4.97634064 0.04167005
H 3.35734906 3.77522255 0.09742038
C -2.44253197 3.19212464 -0.04431332
C -2.48522977 1.76171655 -0.05627154
H -1.24934374 4.97286173 -0.01861958
H -3.36986887 3.76572134 -0.08217562
C 3.76022121 1.09060232 0.11240825
C 5.02434251 1.73872686 -0.04658589
C 3.86551929 -0.32536801 0.33005408
C 6.21365450 1.06691118 0.00114398
H 5.08138078 2.80822292 -0.25061697
C 5.06350689 -0.97560279 0.37807426
H 2.97131032 -0.92272959 0.50697232
H 7.16473451 1.56235848 -0.18160247
H 5.13306166 -2.03789464 0.60543780
C 7.50763576 -1.00160999 0.25960594
C 7.61220023 -2.33200801 -0.19326229
C 8.66652155 -0.37396061 0.75825475
C 8.83184224 -3.00318885 -0.13496511
H 6.74641439 -2.83326070 -0.62927441
C 9.87898066 -1.05939688 0.79935902
H 8.61415671 0.64477461 1.14560068
C 9.99372947 -2.38880000 0.36085348
H 8.88449029 -4.03147904 -0.50496660
H 10.75912462 -0.54703460 1.19916207
C -3.76452406 1.08009263 -0.11679935
C -5.03034330 1.72254461 0.05084204
C -3.86548305 -0.33441905 -0.34546678
C -6.21740208 1.04678909 0.00194339
H -5.09056227 2.79014599 0.26373075
C -5.06122675 -0.98855968 -0.39463123
H -2.96972732 -0.92717595 -0.52979138
H -7.16950149 1.53740127 0.19224335
H -5.12778288 -2.04934354 -0.62958334
C -7.50446291 -1.02523709 -0.26396079
C -7.60044620 -2.35897931 0.17949740
C -8.66939038 -0.39870076 -0.75108475
C -8.81814750 -3.03489324 0.12401266
H -6.72988421 -2.86007704 0.60596810
C -9.87891594 -1.08845832 -0.78915141
H -8.62333359 0.62288591 -1.13166830
C -9.98539879 -2.42173099 -0.35880395
H -8.86438711 -4.06621229 0.48601268
H -10.76369020 -0.57711349 -1.18001144
N 6.27459000 -0.31297845 0.21063048
N -6.27410586 -0.33162729 -0.21770890
C 11.30242783 -3.13437477 0.44527181
H 11.41122212 -3.64783247 1.41760188
H 11.38024922 -3.90491614 -0.33745284
H 12.16278971 -2.45537305 0.34025578
C -11.29405683 -3.16804748 -0.43718056
H -11.47799249 -3.55252199 -1.45646469
H -11.30669564 -4.03227397 0.24430700
H -12.14674759 -2.51987089 -0.17972146
$end
Please provide your complete input file in one piece. Use the </> button to avoid special characters being converted into formatted text.
With RPA=0 (which is the default behavior, you shouldn’t need to set it explicitly) there is no B matrix and you should not get this error message.
Thanks for your reply.
This is my complete input file:
$rem
jobtype opt
exchange b3lyp
basis gen
purecart 11
CIS_STATE_DERIV 1
cis_n_roots 10
cis_singlets false
cis_triplets true
state_analysis true
XC_GRID 000075000302
gui 2
scf_convergence 6
max_scf_cycles 500
mem_total 10000
$end
$molecule
0 1
C 2.47893970 1.76878137 0.05529023
C 1.24788277 1.08542868 0.01974460
C -0.00314249 1.75539977 -0.00128266
C -0.00531774 3.19383591 0.00440011
C 1.23754191 3.88260019 0.03108371
C 2.43184071 3.19910667 0.05431724
H -1.22902673 -0.00918627 -0.00581792
H 1.22806944 -0.00546940 -0.00917271
C -1.25218683 1.08181290 -0.02699979
C -1.25024142 3.87905841 -0.01657285
H 1.23332229 4.97634064 0.04167005
H 3.35734906 3.77522255 0.09742038
C -2.44253197 3.19212464 -0.04431332
C -2.48522977 1.76171655 -0.05627154
H -1.24934374 4.97286173 -0.01861958
H -3.36986887 3.76572134 -0.08217562
C 3.76022121 1.09060232 0.11240825
C 5.02434251 1.73872686 -0.04658589
C 3.86551929 -0.32536801 0.33005408
C 6.21365450 1.06691118 0.00114398
H 5.08138078 2.80822292 -0.25061697
C 5.06350689 -0.97560279 0.37807426
H 2.97131032 -0.92272959 0.50697232
H 7.16473451 1.56235848 -0.18160247
H 5.13306166 -2.03789464 0.60543780
C 7.50763576 -1.00160999 0.25960594
C 7.61220023 -2.33200801 -0.19326229
C 8.66652155 -0.37396061 0.75825475
C 8.83184224 -3.00318885 -0.13496511
H 6.74641439 -2.83326070 -0.62927441
C 9.87898066 -1.05939688 0.79935902
H 8.61415671 0.64477461 1.14560068
C 9.99372947 -2.38880000 0.36085348
H 8.88449029 -4.03147904 -0.50496660
H 10.75912462 -0.54703460 1.19916207
C -3.76452406 1.08009263 -0.11679935
C -5.03034330 1.72254461 0.05084204
C -3.86548305 -0.33441905 -0.34546678
C -6.21740208 1.04678909 0.00194339
H -5.09056227 2.79014599 0.26373075
C -5.06122675 -0.98855968 -0.39463123
H -2.96972732 -0.92717595 -0.52979138
H -7.16950149 1.53740127 0.19224335
H -5.12778288 -2.04934354 -0.62958334
C -7.50446291 -1.02523709 -0.26396079
C -7.60044620 -2.35897931 0.17949740
C -8.66939038 -0.39870076 -0.75108475
C -8.81814750 -3.03489324 0.12401266
H -6.72988421 -2.86007704 0.60596810
C -9.87891594 -1.08845832 -0.78915141
H -8.62333359 0.62288591 -1.13166830
C -9.98539879 -2.42173099 -0.35880395
H -8.86438711 -4.06621229 0.48601268
H -10.76369020 -0.57711349 -1.18001144
N 6.27459000 -0.31297845 0.21063048
N -6.27410586 -0.33162729 -0.21770890
C 11.30242783 -3.13437477 0.44527181
H 11.41122212 -3.64783247 1.41760188
H 11.38024922 -3.90491614 -0.33745284
H 12.16278971 -2.45537305 0.34025578
C -11.29405683 -3.16804748 -0.43718056
H -11.47799249 -3.55252199 -1.45646469
H -11.30669564 -4.03227397 0.24430700
H -12.14674759 -2.51987089 -0.17972146
$end
$basis
H 0
S 3 1.00
13.0107010 0.19682158D-01
1.9622572 0.13796524
0.44453796 0.47831935
S 1 1.00
0.12194962 1.0000000
P 1 1.00
0.8000000 1.0000000
C 0
S 5 1.00
1238.4016938 0.54568832082D-02
186.29004992 0.40638409211D-01
42.251176346 0.18025593888
11.676557932 0.46315121755
3.5930506482 0.44087173314
S 1 1.00
0.40245147363 1.0000000
S 1 1.00
0.13090182668 1.0000000
P 3 1.00
9.4680970621 0.38387871728D-01
2.0103545142 0.21117025112
0.54771004707 0.51328172114
P 1 1.00
0.15268613795 1.0000000
D 1 1.00
0.8000000 1.0000000
N 0
S 5 1.00
1712.8415853 -0.53934125305D-02
257.64812677 -0.40221581118D-01
58.458245853 -0.17931144990
16.198367905 -0.46376317823
5.0052600809 -0.44171422662
S 1 1.00
0.58731856571 1.0000000
S 1 1.00
0.18764592253 1.0000000
P 3 1.00
13.571470233 -0.40072398852D-01
2.9257372874 -0.21807045028
0.79927750754 -0.51294466049
P 1 1.00
0.21954348034 1.0000000
D 1 1.00
1.0000000 1.0000000
$end
A couple of comments:
(1) I’m not sure why you are not using the default grid, which is SG-1 for B3LYP. The (75,302) grid requires a lot of extra time and SG-1 is perfectly fine for TD-B3LYP calculations and about 30% cheaper for this system.
(2) At least on the first geometry, this works fine for me (i.e., the TDDFT iterations and the relaxed density iterations both run to completion). However, I do notice that the first excitation energy is negative. That generally indicates an instability in the ground state. It’s possible that might cause problems in subsequent iterations, and it will definitely be a problem if you set RPA = 1 or 2.
In any case, with the current Q-Chem trunk (basically v. 6.2.1), the input that you provided converged in 6 optimization steps but the first excitation energy remains negative.
Hi,
Thanks for your reply.
Before TDDFT calculations, I also optimized the structure in triplet rather than singlet using DFT and the results show that the triplet is the ground state. I am not sure it makes sense or not. I could not believe that.
Maybe I should do TDDFT from the triplet.
The negative excitation energy that I got was about -0.5 eV. I think this would be consistent with a triplet ground state but the TDA-TDDFT optimization did converge (on the singlet S1 surface) for me.