CCL: Problem SCF convergence(energy oscillation) in extended pi
system/G03
- From: "Ronald C. Bakus"
<rbakus*|*chem.ucsb.edu>
- Subject: CCL: Problem SCF convergence(energy oscillation) in
extended pi system/G03
- Date: Sat, 28 Nov 2009 17:05:18 -0500
Sent to CCL by: "Ronald C. Bakus" [rbakus!=!chem.ucsb.edu]
Im having some issues with a problem convergence case for a extended pi system.
Without diffuse functions, convergence is fine, however, upon addition of
diffuse functions the optimization will get close to completing, but on one of
the last scf cycles, the energy will decrease and then oscillate around
convergence. The homo-lumo gap is small, slightly less than .2H. I have already
tried various combinations of the standard ways of dealing with problem scf (qc,
vshift=x (x=150,300,500,1000), nodiis, novaracc, optimization+freq calc without
diffuse as starting point for diffuse, etc.) with no success. I was hoping to
perhaps get some input on other ways to deal with the problem. The diffuse
functions will be important to later phases of the calculations.
Sample Input (I have tried both syn and anti conformers of the dimethylamino
groups)
------
%chk=dsb.chk
%mem=20MW
#p opt b3lyp/6-31+g(d,p) geom=connectivity int=ultrafine cphf=ultrafine
formcheck
dsb14 opt
0 1
C
C 1 B1
C 2 B2 1 A1
C 3 B3 2 A2 1 D1
C 4 B4 3 A3 2 D2
C 5 B5 4 A4 3 D3
H 1 B6 2 A5 3 D4
H 2 B7 1 A6 6 D5
H 4 B8 3 A7 2 D6
H 5 B9 4 A8 3 D7
C 3 B10 2 A9 1 D8
H 11 B11 3 A10 2 D9
C 11 B12 3 A11 2 D10
H 13 B13 11 A12 3 D11
C 13 B14 11 A13 3 D12
C 15 B15 13 A14 11 D13
C 15 B16 13 A15 11 D14
C 16 B17 15 A16 13 D15
H 16 B18 15 A17 13 D16
C 17 B19 15 A18 13 D17
H 17 B20 15 A19 13 D18
C 18 B21 16 A20 15 D19
H 18 B22 16 A21 15 D20
H 20 B23 17 A22 15 D21
C 22 B24 18 A23 16 D22
H 25 B25 22 A24 18 D23
C 25 B26 22 A25 18 D24
H 27 B27 25 A26 22 D25
C 27 B28 25 A27 22 D26
C 29 B29 27 A28 25 D27
C 29 B30 27 A29 25 D28
C 30 B31 29 A30 27 D29
H 30 B32 29 A31 27 D30
C 31 B33 29 A32 27 D31
H 31 B34 29 A33 27 D32
C 32 B35 30 A34 29 D33
H 32 B36 30 A35 29 D34
H 34 B37 31 A36 29 D35
N 6 B38 5 A37 4 D36
N 36 B39 32 A38 30 D37
C 40 B40 36 A39 32 D38
H 41 B41 40 A40 36 D39
H 41 B42 40 A41 36 D40
H 41 B43 40 A42 36 D41
C 40 B44 36 A43 32 D42
H 45 B45 40 A44 36 D43
H 45 B46 40 A45 36 D44
H 45 B47 40 A46 36 D45
C 39 B48 6 A47 5 D46
H 49 B49 39 A48 6 D47
H 49 B50 39 A49 6 D48
H 49 B51 39 A50 6 D49
C 39 B52 6 A51 5 D50
H 53 B53 39 A52 6 D51
H 53 B54 39 A53 6 D52
H 53 B55 39 A54 6 D53
B1 1.38590600
B2 1.40879299
B3 1.40676154
B4 1.38827161
B5 1.41292513
B6 1.08298050
B7 1.08583864
B8 1.08754627
B9 1.08285660
B10 1.45944010
B11 1.08912863
B12 1.35168559
B13 1.08891058
B14 1.46036881
B15 1.41101301
B16 1.40955110
B17 1.38649352
B18 1.08745064
B19 1.38650055
B20 1.08563046
B21 1.40957879
B22 1.08563312
B23 1.08745466
B24 1.46038208
B25 1.08891491
B26 1.35170500
B27 1.08912993
B28 1.45944392
B29 1.40677707
B30 1.40881876
B31 1.38826824
B32 1.08755006
B33 1.38589746
B34 1.08584524
B35 1.41292195
B36 1.08285687
B37 1.08298484
B38 1.38847165
B39 1.38841623
B40 1.45260430
B41 1.09097759
B42 1.10130937
B43 1.09581331
B44 1.45285452
B45 1.09097407
B46 1.09576437
B47 1.10121929
B48 1.45286246
B49 1.09098248
B50 1.10122787
B51 1.09575774
B52 1.45262017
B53 1.09098468
B54 1.09579664
B55 1.10131866
A1 122.07360923
A2 116.25323549
A3 122.52104756
A4 120.89016562
A5 118.44193028
A6 118.09314223
A7 118.89576382
A8 118.63570829
A9 124.25260979
A10 114.09091838
A11 127.48313332
A12 118.61687356
A13 127.13426723
A14 119.07045476
A15 124.12563764
A16 122.03442793
A17 118.76061142
A18 121.16247464
A19 119.98708840
A20 121.16222854
A21 118.85028804
A22 119.20697504
A23 124.12861653
A24 114.24477657
A25 127.13686366
A26 118.42466374
A27 127.48931804
A28 119.49046853
A29 124.25717650
A30 122.52172015
A31 118.89429417
A32 122.07417140
A33 119.83267571
A34 120.89096115
A35 118.63484888
A36 118.44040512
A37 121.62197526
A38 121.62236490
A39 119.34902804
A40 109.13960300
A41 112.95155437
A42 111.01772561
A43 119.49930105
A44 109.10238405
A45 111.07362683
A46 112.96782739
A47 119.49517384
A48 109.10177009
A49 112.97116251
A50 111.06987287
A51 119.34521560
A52 109.13771153
A53 111.01169226
A54 112.95688048
D1 -0.35125191
D2 0.32638204
D3 0.40233558
D4 179.48620457
D5 -179.90506437
D6 -179.42169103
D7 -179.52106898
D8 180.00000000
D9 178.40429122
D10 -1.82780326
D11 -0.31757066
D12 179.89196744
D13 178.73985841
D14 -1.28157819
D15 -179.92043875
D16 -0.00000000
D17 179.91842635
D18 -0.19884610
D19 -0.05473033
D20 179.90530662
D21 179.97520249
D22 -179.96404995
D23 -179.65549459
D24 0.42839517
D25 0.19711844
D26 -179.94034630
D27 -179.19548240
D28 1.14931637
D29 -179.94453526
D30 -0.22485722
D31 179.95511206
D32 0.34504623
D33 -0.42074545
D34 179.50779600
D35 -179.50941383
D36 178.51739236
D37 -178.52921489
D38 171.94094710
D39 178.43928000
D40 -61.14986272
D41 60.18975765
D42 11.63000000
D43 -178.68286485
D44 -60.46741792
D45 60.95449961
D46 170.08048307
D47 178.67201365
D48 -60.96543365
D49 60.45777828
D50 9.82506217
D51 -178.40320889
D52 -60.16058276
D53 61.18077952
1 2 2.0 6 1.5 7 1.0
2 3 1.5 8 1.0
3 4 1.5 11 1.0
4 5 1.5 9 1.0
5 6 1.5 10 1.0
6 39 1.0
7
8
9
10
11 12 1.0 13 2.0
12
13 14 1.0 15 1.0
14
15 16 1.5 17 1.5
16 18 1.5 19 1.0
17 20 1.5 21 1.0
18 22 1.5 23 1.0
19
20 22 1.5 24 1.0
21
22 25 1.0
23
24
25 26 1.0 27 2.0
26
27 28 1.0 29 1.0
28
29 30 1.5 31 1.5
30 32 1.5 33 1.0
31 34 2.0 35 1.0
32 36 1.5 37 1.0
33
34 36 1.5 38 1.0
35
36 40 1.0
37
38
39 49 1.0 53 1.0
40 41 1.0 45 1.0
41 42 1.0 43 1.0 44 1.0
42
43
44
45 46 1.0 47 1.0 48 1.0
46
47
48
49 50 1.0 51 1.0 52 1.0
50
51
52
53 54 1.0 55 1.0 56 1.0
54
55
56
-----
I hope that someone far brighter than me has a suggestion, I have been fighting
with this for 2 weeks.
Ron Bakus
rbakus _ chem.ucsb.edu
UCSB