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标题: orca计算含自由基中间体SCF不收敛 [打印本页]

作者
Author: YjLiu 时间: 2021-5-20 10:20
标题: orca计算含自由基中间体SCF不收敛
体系是个含有自由基的有机物种（含C F O）开壳层体系20个原子，高斯优化得到的结果，高斯计算单点也能正常收敛。
某次尝试关键词如下：
|  1> ! DLPNO-CCSD(T) tightPNO Extrapolate(2/3,cc) cc-pVTZ/C tightSCF noautostart miniprint nopop
|  2> %mdci
|  3> maxiter 100
|  4> MaxDIIS 15
|  5> end
|  6> %maxcore  6034
|  7> %pal nprocs 14 end
|  8> * xyz 0 2
曾多次不收敛，尝试了KDIIS，slowconv和veryslowconv，高斯初猜，都无法收敛。有的SCF ITERATIONS不收敛，有的第二次OPEN-SHELL COUPLED CLUSTER ITERATIONS不收敛。不收敛的信息如下：
----------------------------------------------------------
                  OPEN-SHELL COUPLED CLUSTER ITERATIONS
----------------------------------------------------------

Number of PNO amplitudes to be optimized       ...       2561818
Number of canonical amplitudes for strong pairs ...    1053692039
Untruncated number of canonical amplitudes    ...    1688310639

Iter    E(tot)          E(Corr)       Delta-E       Residual    Time
  0  -1500.391787960    -3.953207921    0.004513804    0.021067115  250.01
                        *** Turning on DIIS ***
  1  -1500.464461751    -4.025881712    -0.072673792    0.013792192  226.22
  2  -1500.541994868    -4.103414829    -0.077533117    0.006655934  232.38
  3  -1500.556546936    -4.117966897    -0.014552068    0.003634285  230.80
  4  -1500.561972403    -4.123392364    -0.005425467    0.003135378  232.63
  5  -1500.562891572    -4.124311533    -0.000919169    0.002083256  236.55
  6  -1500.563057753    -4.124477714    -0.000166181    0.001511738  253.47
  7  -1500.563236987    -4.124656948    -0.000179234    0.000840184  247.26
  8  -1500.563350933    -4.124770893    -0.000113945    0.000360896  229.99
  9  -1500.563362411    -4.124782371    -0.000011478    0.000269370  260.41
10  -1500.563376121    -4.124796082    -0.000013710    0.000273667  230.67
11  -1500.563378033    -4.124797993    -0.000001912    0.000277174  280.42
12  -1500.563377314    -4.124797274    0.000000719    0.000280224  233.96
13  -1500.563377382    -4.124797342    -0.000000068    0.000280633  233.13
14  -1500.563377423    -4.124797383    -0.000000041    0.000280919 1804.86
15  -1500.563377451    -4.124797412    -0.000000029    0.000281137  235.72
16  -1500.563377250    -4.124797211    0.000000201    0.000281311  234.07
17  -1500.563377323    -4.124797283    -0.000000073    0.000281451  233.77
18  -1500.563377750    -4.124797710    -0.000000427    0.000281563  233.56
19  -1500.563378015    -4.124797976    -0.000000266    0.000281656  233.18
20  -1500.563377823    -4.124797784    0.000000192    0.000281737  245.15
21  -1500.563377679    -4.124797640    0.000000144    0.000281803  231.79
22  -1500.563377441    -4.124797402    0.000000238    0.000281862  249.96
23  -1500.563377790    -4.124797750    -0.000000348    0.000282027  228.30
24  -1500.563377869    -4.124797830    -0.000000080    0.000282081  251.61
25  -1500.563377631    -4.124797592    0.000000238    0.000282219  253.27
26  -1500.563377546    -4.124797506    0.000000086    0.000282164  213.25
27  -1500.563377874    -4.124797835    -0.000000329    0.000283137  231.45
28  -1500.563377891    -4.124797851    -0.000000017    0.000283112  290.21
29  -1500.563377903    -4.124797863    -0.000000012    0.000283073  236.95
30  -1500.563377911    -4.124797871    -0.000000008    0.000283030  250.74
31  -1500.563377916    -4.124797877    -0.000000005    0.000282986  230.29
32  -1500.563377920    -4.124797880    -0.000000004    0.000282944  227.06
33  -1500.563377922    -4.124797882    -0.000000002    0.000282905  233.40
34  -1500.563377922    -4.124797883    -0.000000001    0.000282871  244.53
35  -1500.563377860    -4.124797821    0.000000062    0.000284242  228.32
36  -1500.563377860    -4.124797821    0.000000000    0.000284214  233.03
37  -1500.563377866    -4.124797826    -0.000000006    0.000284191  246.63
38  -1500.563377881    -4.124797841    -0.000000015    0.000284172  229.00
39  -1500.563377879    -4.124797840    0.000000001    0.000284146  234.86
40  -1500.563377874    -4.124797835    0.000000005    0.000284124  241.88
41  -1500.563377877    -4.124797837    -0.000000002    0.000284099  236.21
42  -1500.563377880    -4.124797840    -0.000000003    0.000284074  243.33
43  -1500.563377878    -4.124797838    0.000000002    0.000284041  273.28
44  -1500.563377876    -4.124797837    0.000000002    0.000284012  286.30
45  -1500.563377875    -4.124797836    0.000000001    0.000283986  282.34
46  -1500.563377874    -4.124797835    0.000000001    0.000283963  253.57
47  -1500.563377873    -4.124797834    0.000000001    0.000283943  240.16
48  -1500.563377872    -4.124797833    0.000000001    0.000283925  270.33
49  -1500.563377872    -4.124797832    0.000000001    0.000283910  253.10
50  -1500.563377969    -4.124797930    -0.000000097    0.000285695  243.82
51  -1500.563377929    -4.124797890    0.000000040    0.000285351  245.71
52  -1500.563377938    -4.124797899    -0.000000009    0.000285432  231.51
53  -1500.563377948    -4.124797909    -0.000000009    0.000285520 1195.86
54  -1500.563377957    -4.124797918    -0.000000009    0.000285614 2676.75
55  -1500.563377967    -4.124797928    -0.000000010    0.000285716  360.46
56  -1500.563377979    -4.124797939    -0.000000011    0.000285823  257.93
57  -1500.563377982    -4.124797942    -0.000000003    0.000285859  262.28
58  -1500.563377993    -4.124797954    -0.000000011    0.000285974  299.40
59  -1500.563378002    -4.124797962    -0.000000008    0.000286058  238.23
60  -1500.563378016    -4.124797976    -0.000000014    0.000286197  265.80
61  -1500.563378030    -4.124797991    -0.000000014    0.000286339  242.19
62  -1500.563378049    -4.124798010    -0.000000019    0.000286529  231.73
63  -1500.563378071    -4.124798032    -0.000000022    0.000286747  230.08
64  -1500.563378099    -4.124798060    -0.000000028    0.000287026  254.17
65  -1500.563378133    -4.124798093    -0.000000034    0.000287364  238.41
66  -1500.563378109    -4.124798070    0.000000023    0.000287163  241.11
67  -1500.563378133    -4.124798094    -0.000000024    0.000287374  228.61
68  -1500.563378156    -4.124798116    -0.000000022    0.000287569  238.20
69  -1500.563378159    -4.124798119    -0.000000003    0.000287595  252.72
70  -1500.563378182    -4.124798142    -0.000000023    0.000287795  234.99
71  -1500.563378187    -4.124798147    -0.000000005    0.000287840  244.00
72  -1500.563378210    -4.124798171    -0.000000023    0.000288040  227.93
73  -1500.563378220    -4.124798180    -0.000000010    0.000288126  243.77
74  -1500.563378243    -4.124798204    -0.000000024    0.000288329  237.58
75  -1500.563378256    -4.124798217    -0.000000013    0.000288443  242.60
76  -1500.563378280    -4.124798241    -0.000000024    0.000288647  228.03
77  -1500.563378294    -4.124798255    -0.000000014    0.000288768  238.40
78  -1500.563378317    -4.124798278    -0.000000023    0.000288961  232.69
79  -1500.563378329    -4.124798289    -0.000000012    0.000289062  237.73
80  -1500.563378347    -4.124798308    -0.000000019    0.000289218  236.02
81  -1500.563378353    -4.124798314    -0.000000005    0.000289263  231.97
82  -1500.563378382    -4.124798343    -0.000000029    0.000289501  222.81
83  -1500.563378386    -4.124798346    -0.000000004    0.000289530  419.05
84  -1500.563378413    -4.124798374    -0.000000028    0.000289754  284.79
85  -1500.563378421    -4.124798382    -0.000000008    0.000289816  251.48
86  -1500.563378447    -4.124798407    -0.000000026    0.000290023  269.25
87  -1500.563378458    -4.124798418    -0.000000011    0.000290113  242.51
88  -1500.563378482    -4.124798442    -0.000000024    0.000290304  246.03
89  -1500.563378495    -4.124798455    -0.000000013    0.000290410  237.12
90  -1500.563378516    -4.124798477    -0.000000022    0.000290585  241.84
91  -1500.563378530    -4.124798491    -0.000000014    0.000290696  254.16
92  -1500.563378550    -4.124798511    -0.000000020    0.000290855  232.02
93  -1500.563378564    -4.124798525    -0.000000014    0.000290968  230.89
94  -1500.563378582    -4.124798543    -0.000000018    0.000291113  226.81
95  -1500.563378598    -4.124798559    -0.000000015    0.000291235  230.62
96  -1500.563378615    -4.124798576    -0.000000018    0.000291375  219.93
97  -1500.563378634    -4.124798595    -0.000000019    0.000291523  249.70
98  -1500.563378648    -4.124798609    -0.000000014    0.000291636  229.61
99  -1500.563378671    -4.124798632    -0.000000023    0.000291815  285.24
            --- The CCSD iterations have NOT converged ---

感觉残差没有收敛的趋势，请问各位老师这种怎么解决，谢谢！

作者
Author: zjxitcc 时间: 2021-5-20 10:38
本帖最后由 zjxitcc 于 2021-5-20 10:40 编辑

非也。“不收敛”种类非常多，例如你这里要区分 SCF不收敛和 CC振幅迭代不收敛，这样才能对症下药。若你CC振幅迭代不收敛，你却用一堆SCF不收敛的关键词，那当然几乎无效了。你想说SCF不收敛，你就贴出SCF不收敛的截图。你当前贴的内容是CC振幅迭代不收敛，但它快收敛了，增大振幅迭代圈数也无妨。

作者
Author: YjLiu 时间: 2021-5-20 11:05

zjxitcc 发表于 2021-5-20 10:38
非也。“不收敛”种类非常多，例如你这里要区分 SCF不收敛和 CC振幅迭代不收敛，这样才能对症下药。若你CC ...

嗯嗯，我确实是搞混了。之前有SCF不收敛的情况但是好像都解决了，目前来看就是CC迭代不收敛，感觉这个上边来看的话残差这一项好像没有收敛的趋势呀，之前试过150圈的，这项也是一直在e-3~e-4，感觉没有收敛的趋势

作者
Author: zjxitcc 时间: 2021-5-20 11:20
本帖最后由 zjxitcc 于 2021-5-20 11:21 编辑

YjLiu 发表于 2021-5-20 11:05
嗯嗯，我确实是搞混了。之前有SCF不收敛的情况但是好像都解决了，目前来看就是CC迭代不收敛，感觉这个上 ...

哦，你的Residual和Time这些表头对应不上相应的列。。。是因为你直接复制的缘故，怪不得我咋看不出不收敛

作者
Author: YjLiu 时间: 2021-5-20 11:42

zjxitcc 发表于 2021-5-20 11:20
哦，你的Residual和Time这些表头对应不上相应的列。。。是因为你直接复制的缘故，怪不得我咋看不出不收敛

对的对的。老师可有好的解决办法呀

作者
Author: wzkchem5 时间: 2021-5-20 14:53

YjLiu 发表于 2021-5-20 04:42
对的对的。老师可有好的解决办法呀

加大CCSD迭代次数；加大或减小maxdiis（是%mdci里的maxdiis，不是%scf里的maxdiis）
另外注意一下体系有没有显著的多参考态性质，CCSD收敛困难的体系往往是多参考态的，此时CCSD(T)结果不靠谱

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