请教稀土配合物优化失败如何解决

bomsaude · 发表于 Post on 2014-12-17 18:33:22

本帖最后由 bomsaude 于 2014-12-17 18:59 编辑

接触高斯有半年了，原先按书上和网上的一些小分子进行了了一些演练，现在想练习一些大一点的分子，几何优化就不收敛了。稀土配合物是最常见的Eu(TTA)3phen，C H O N F采用6-31g基组，S采用6-31g(d)基组，Eu采用赝势基组，输入文件如下，不知道有什么不对或不合适的地方？看到文献上写All the molecular structures were fully optimized in the gas-phase without symmetry restrictions by the gradient procedure，那么关键词中用不用加nosymm?

%chk=euttaphen.chk
# opt b3lyp/genecp geom=connectivity Opt of EuTTAphen 0 1
Eu 1.46400000 9.32300000 4.44890000
H 6.51600000 12.70290000 9.83990000
H 6.66190000 15.49600000 3.37000000
H 5.66000000 10.54290000 -2.32690000
S 4.34400000 11.48090000 7.97790000
S 4.48500000 13.32190000 3.64000000
S 4.01100000 9.72300000 0.15300000
F -2.73490000 9.45400000 7.36390000
F -1.72290000 9.15790000 9.21190000
F -1.76290000 7.65590000 7.77890000
F -1.68790000 10.32790000 0.96400000
F -2.36300000 11.83600000 2.13100000
F -1.23700000 12.29400000 0.49000000
F -0.96600000 5.24890000 3.32690000
F -0.68400000 5.14900000 1.20990000
F -1.99290000 6.57890000 2.03690000
O 2.22190000 10.31900000 6.44800000
O -0.26500000 9.15490000 6.05600000
O 2.37990000 11.40190000 3.79000000
O -0.19500000 10.50090000 3.25400000
O 0.23600000 7.58990000 3.45100000
O 2.34690000 8.94290000 2.29990000
N 3.96890000 8.71100000 4.65500000
N 2.04700000 7.08900000 5.64100000
C 1.83000000 10.49390000 7.61700000
C 4.33600000 7.48400000 5.11200000
C 0.52400000 10.10990000 8.05590000
H 0.27200000 10.32600000 8.92390000
C -0.37200000 9.44590000 7.27090000
C 2.77800000 11.08090000 8.55790000
C 2.12800000 12.21400000 2.85290000
C 0.96500000 12.18590000 2.07390000
H 0.90500000 12.76290000 1.34690000
C 3.33190000 6.63100000 5.63790000
C -1.64590000 8.96100000 7.93600000
C 1.11400000 7.21490000 1.30600000
H 1.05200000 6.65590000 0.56490000
C 4.92100000 9.49600000 4.14100000
H 4.67300000 10.30700000 3.75990000
C 1.10890000 6.28500000 6.12500000
H 0.23300000 6.59690000 6.14400000
C 3.86600000 11.92090000 10.43500000
H 3.95100000 12.19200000 11.32090000
C 2.68100000 11.34690000 9.86400000
H 1.91300000 11.17390000 10.35990000
C -0.11300000 11.33090000 2.33800000
C 6.62990000 7.94090000 4.60700000
H 7.52890000 7.70200000 4.59790000
C 5.98890000 5.75390000 5.53890000
H 6.86200000 5.43790000 5.48090000
C 3.67390000 5.36590000 6.08190000
C 5.68990000 7.04390000 5.08300000
C 2.05690000 8.21000000 1.29090000
C 4.82000000 12.00790000 9.51990000
C 0.26300000 7.00390000 2.34690000
C 6.26400000 9.14790000 4.16090000
H 6.90800000 9.75090000 3.86300000
C 3.13700000 14.27290000 1.69700000
H 2.49690000 14.38100000 1.03090000
C 2.66500000 4.56790000 6.59100000
H 2.87190000 3.72500000 6.92800000
C 5.04800000 4.97600000 6.05490000
H 5.29000000 4.15090000 6.40800000
C 1.35700000 5.00300000 6.60500000
H 0.67000000 4.46190000 6.92190000
C -1.37300000 11.42090000 1.47100000
C -0.82200000 5.90800000 2.22500000
C 3.10990000 13.26200000 2.61600000
C 2.85400000 8.02890000 -1.14790000
H 2.23090000 7.38900000 -1.40600000
C 5.03690000 14.71190000 2.83900000
C 4.25900000 15.14790000 1.86900000
H 4.41390000 15.91600000 1.36790000
C 4.42490000 9.46190000 -1.53290000
C 3.65390000 8.46100000 -1.93200000
H 3.72790000 8.10690000 -2.79000000
C 2.88100000 8.48400000 0.08400000 1 17 1.0 18 1.0 19 1.0 20 1.0 21 1.0 22 1.0 23 1.0 24 1.0
2 54 1.0
3 71 1.0
4 74 1.0
5 30 1.0 54 1.0
6 68 1.0 71 1.0
7 74 1.0 77 1.0
8 35 1.0
9 35 1.0
10 35 1.0
11 66 1.0
12 66 1.0
13 66 1.0
14 67 1.0
15 67 1.0
16 67 1.0
17 25 1.0
18 29 1.0
19 31 1.0
20 46 1.0
21 55 1.0
22 53 1.0
23 26 1.0 38 1.0
24 34 1.0 40 1.0
25 27 1.0 30 1.0
26 34 1.0 52 1.0
27 28 1.0 29 1.0
28
29 35 1.0
30 44 1.0
31 32 1.0 68 1.0
32 33 1.0 46 1.0
33
34 51 1.0
35
36 37 1.0 53 1.0 55 1.0
37
38 39 1.0 56 1.0
39
40 41 1.0 64 1.0
41
42 43 1.0 44 1.0 54 1.0
43
44 45 1.0
45
46 66 1.0
47 48 1.0 52 1.0 56 1.0
48
49 50 1.0 52 1.0 62 1.0
50
51 60 1.0 62 1.0
52
53 77 1.0
54
55 67 1.0
56 57 1.0
57
58 59 1.0 68 1.0 72 1.0
59
60 61 1.0 64 1.0
61
62 63 1.0
63
64 65 1.0
65
66
67
68
69 70 1.0 75 1.0 77 1.0
70
71 72 1.0
72 73 1.0
73
74 75 1.0
75 76 1.0
76
77C H O F N 0
6-31g
****
S 0
6-31g(d)
****
Eu 0
S 5 1.00
70059.4200000 0.0000970
10776.2350000 0.0007070
2482.4901000 0.0033620
702.1526000 0.0102060
216.7926000 0.0165970
S 1 1.00
41.4950000 1.0000000
S 1 1.00
29.4969000 1.0000000
S 1 1.00
15.0309000 1.0000000
S 1 1.00
3.7772000 1.0000000
S 1 1.00
1.9219000 1.0000000
S 1 1.00
0.7131000 1.0000000
S 1 1.00
0.3097000 1.0000000
S 1 1.00
0.0549000 1.0000000
S 1 1.00
0.0227000 1.0000000
P 6 1.00
4058.0207000 0.0000480
1023.3259000 0.0003570
339.3852000 0.0016870
122.3485000 0.0056930
29.0558000 0.0723980
20.6269000 -0.0468070
P 1 1.00
14.6179000 1.0000000
P 1 1.00
5.4444000 1.0000000
P 1 1.00
2.7414000 1.0000000
P 1 1.00
1.2283000 1.0000000
P 1 1.00
0.5769000 1.0000000
P 1 1.00
0.2489000 1.0000000
P 1 1.00
0.0800000 1.0000000
D 6 1.00
389.0841000 0.0005340
117.7602000 0.0042580
44.9869000 0.0171600
22.8599000 0.0124270
7.8331000 0.2704160
4.1134000 0.4452720
D 1 1.00
2.0999000 1.0000000
D 1 1.00
1.0043000 1.0000000
D 1 1.00
0.3422000 1.0000000
D 1 1.00
0.1051000 1.0000000
F 5 1.00
128.2341000 0.0034240
46.2685000 0.0343130
20.7366000 0.1231940
9.4479000 0.2518240
4.3149000 0.3512920
F 1 1.00
1.9121000 1.0000000
F 1 1.00
0.7897000 1.0000000
F 1 1.00
0.2859000 1.0000000
G 4 1.00
20.7366000 0.0265160
9.4479000 0.0990660
4.3149000 0.2133780
1.9121000 0.4537130
G 1 1.00
0.7897000 1.0000000
G 1 1.00
0.2859000 1.0000000
**** Eu 0
ECP28MWB 5 28
H-Komponente
1
2 1.000000 0.000000
S-H
1
2 23.471384 607.659331
P-H
1
2 16.772479 264.385476
D-H
1
2 13.981343 115.381375
F-H
1
2 23.962888 -49.400794
G-H
1
2 21.232458 -26.748273

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log文件的部分内容如下

......
There are 685 symmetry adapted basis functions of A symmetry.
Integral buffers will be 131072 words long.
Raffenetti 2 integral format.
Two-electron integral symmetry is turned on.
685 basis functions, 1685 primitive gaussians, 723 cartesian basis functions
231 alpha electrons 231 beta electrons
nuclear repulsion energy 11089.1497305945 Hartrees.
NAtoms= 77 NActive= 77 NUniq= 77 SFac= 1.00D+00 NAtFMM= 50 NAOKFM=T Big=T
One-electron integrals computed using PRISM.
1 Symmetry operations used in ECPInt.
ECPInt: NShTT= 29890 NPrTT= 254997 LenC2= 21948 LenP2D= 80677.
LDataN: DoStor=T MaxTD1= 9 Len= 602
NBasis= 685 RedAO= T NBF= 685
NBsUse= 685 1.00D-06 NBFU= 685
Defaulting to unpruned grid for atomic number 63.
Harris functional with IExCor= 402 diagonalized for initial guess.
ExpMin= 2.27D-02 ExpMax= 7.01D+04 ExpMxC= 1.08D+04 IAcc=3 IRadAn= 0 AccDes= 0.00D+00
HarFok: IExCor= 402 AccDes= 0.00D+00 IRadAn= 0 IDoV= 1
ScaDFX= 1.000000 1.000000 1.000000 1.000000
Defaulting to unpruned grid for atomic number 63.
Defaulting to unpruned grid for atomic number 63.
FoFCou: FMM=F IPFlag= 0 FMFlag= 100000 FMFlg1= 2001
NFxFlg= 0 DoJE=T BraDBF=F KetDBF=T FulRan=T
Omega= 0.000000 0.000000 1.000000 0.000000 0.000000 ICntrl= 500 IOpCl= 0
NMat0= 1 NMatS0= 1 NMatT0= 0 NMatD0= 1 NMtDS0= 0 NMtDT0= 0
I1Cent= 4 NGrid= 0.
......
The electronic state of the initial guess is 1-A.
Requested convergence on RMS density matrix=1.00D-08 within 128 cycles.
Requested convergence on MAX density matrix=1.00D-06.
Requested convergence on energy=1.00D-06.
No special actions if energy rises.
Defaulting to unpruned grid for atomic number 63.
Defaulting to unpruned grid for atomic number 63.
EnCoef did 3 forward-backward iterations
EnCoef did 100 forward-backward iterations
EnCoef did 100 forward-backward iterations
EnCoef did 100 forward-backward iterations
EnCoef did 4 forward-backward iterations
Restarting incremental Fock formation.
Matrix for removal 4 Erem= -4537.45091694709 Crem= 0.000D+00
Matrix for removal 3 Erem= -4639.05934792761 Crem= 0.000D+00
Matrix for removal 3 Erem= -4702.55800949193 Crem= 0.000D+00
Matrix for removal 3 Erem= -4723.24313399146 Crem= 0.000D+00
Restarting incremental Fock formation.
Restarting incremental Fock formation.
Restarting incremental Fock formation.
Restarting incremental Fock formation.
Restarting incremental Fock formation.
>>>>>>>>>> Convergence criterion not met.
SCF Done: E(RB3LYP) = -4746.74628519 A.U. after 129 cycles
Convg = 0.7593D-05 -V/T = 2.0847
Convergence failure -- run terminated.
Error termination via Lnk1e in /home/user/g09/l502.exe at Wed Dec 17 00:33:33 2014.
Job cpu time: 0 days 15 hours 52 minutes 36.1 seconds.
File lengths (MBytes): RWF= 250 Int= 0 D2E= 0 Chk= 8 Scr= 1

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出现这种情况，我应该增大循环次数还是修改收敛标准？望有经验的人给予指点，谢谢了！

sobereva · 发表于 Post on 2014-12-17 20:03:55

如果初始结构本身就没有对称性就不用加nosymm
解决SCF不收敛没有万能的办法，有可能解决此问题的方法在此贴有汇总：
解决SCF不收敛问题的方法
http://sobereva.com/61
应结合实际情况，将其中的方法挨个试试，或者组合使用。增大循环次数是最没用、还白浪费计算时间的做法。

过渡金属体系不容易收敛是正常的。

另外应当用#P，输出迭代的细节信息，以便于监控收敛到了什么程度，这有助于选择合适的方法帮助收敛。

bomsaude · 发表于 Post on 2014-12-18 00:02:47

sobereva 发表于 2014-12-17 20:03
如果初始结构本身就没有对称性就不用加nosymm
解决SCF不收敛没有万能的办法，有可能解决此问题的方法在此 ...

谢谢，我按照您说的方法试试看。

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[新手求助] 请教稀土配合物优化失败如何解决