计算化学公社

标题: orca寻过渡态问题 [打印本页]

作者
Author: dingliping1108 时间: 2016-6-12 21:51
标题: orca寻过渡态问题
  请教各位老师，在用orca寻找过渡态的时候，已经循环到了最大次数The optimization did not converge but reached the maximum number of optimization cycles，然后开始继续算hess矩阵，就变成这个样子，每次迭代次数变成127次，刚开始迭代的时候时候只有20次，这是什么情况？？遇到这种优化已经达到最大次数的情况，我是不是应该把输出的xyz坐标作为起始坐标继续优化？
下面这个是寻找过渡态循环已经达到最大次数时候的：
                        *E R R O R*
      ******************       ******************
      *** THE CP-SCF CALCULATION IS UNCONVERGED ***
      *********************************************

IBatch 2 (of 16)
  Iteration 0: MaxR= 366118146.064492702
  Iteration 1: MaxR= 263452419718.335601807
  Iteration 2: MaxR= 9827284646.820165634
  Iteration 3: MaxR= 173379835.379316777
  Iteration 4: MaxR= 125687871.356145501
  Iteration 5: MaxR= 32979782.210532825
  Iteration 6: MaxR= 17442801.077132579
  Iteration 7: MaxR= 14589991.600098109
  Iteration 8: MaxR= 12930013.305662001
  Iteration 9: MaxR= 12266559.074612424
  Iteration  10: MaxR= 11835171.619441474
  Iteration  11: MaxR= 11310407.942339353
  Iteration  12: MaxR= 10513590.991512857
  Iteration  13: MaxR= 8641144.886586534
  Iteration  14: MaxR= 7856646.272673567
  Iteration  15: MaxR= 6625967.010963998
  Iteration  16: MaxR= 3456885.811271547
  Iteration  17: MaxR= 2001338.703249060
  Iteration  18: MaxR= 1461598.629728698
  Iteration  19: MaxR= 950151.015511778
  Iteration  20: MaxR= 677081.757965383
  Iteration  21: MaxR= 1015825.732297299
  Iteration  22: MaxR= 356524.834037983
  Iteration  23: MaxR= 248816.267435288
  Iteration  24: MaxR= 389044.242098729
  Iteration  25: MaxR= 365823.070272421
  Iteration  26: MaxR= 484281.970997477
  Iteration  27: MaxR= 236571.878747704
  Iteration  28: MaxR= 283110.499614882
  Iteration  29: MaxR= 248222.054535606
  Iteration  30: MaxR= 185836.864147385
  Iteration  31: MaxR= 174272.467660890
  Iteration  32: MaxR= 417176.665740449
  Iteration  33: MaxR= 457043.431577427
  Iteration  34: MaxR= 327456.166611189
  Iteration  35: MaxR= 131724.705412480
  Iteration  36: MaxR= 93030.500700971
  Iteration  37: MaxR= 90989.941939683
  Iteration  38: MaxR= 125757.183896882
  Iteration  39: MaxR= 103067.700535212
  Iteration  40: MaxR= 43093.557196991
  Iteration  41: MaxR= 60467.394031611
  Iteration  42: MaxR= 236616.635742391
  Iteration  43: MaxR= 84187.170340845
  Iteration  44: MaxR= 25692.672674667
  Iteration  45: MaxR= 35348.227350805
  Iteration  46: MaxR= 68527.923168817
  Iteration  47: MaxR= 90902.533694983
  Iteration  48: MaxR= 43306.391465010
  Iteration  49: MaxR= 73177.178350090
  Iteration  50: MaxR= 34761.311755889
  Iteration  51: MaxR= 32641.577822956
  Iteration  52: MaxR= 36896.566657045
  Iteration  53: MaxR= 39966.103999617
  Iteration  54: MaxR= 27421.521330514
  Iteration  55: MaxR= 38583.849002167
  Iteration  56: MaxR= 19613.281409879
  Iteration  57: MaxR= 17559.089005474
  Iteration  58: MaxR= 93550.005533430
  Iteration  59: MaxR= 93783.014834478
  Iteration  60: MaxR= 54664.994480600
  Iteration  61: MaxR= 41100.142730492
  Iteration  62: MaxR= 43716.984547994
  Iteration  63: MaxR= 44135.457170356
  Iteration  64: MaxR= 23973.869329839
  Iteration  65: MaxR= 18689.830226593
  Iteration  66: MaxR= 17417.657642590
  Iteration  67: MaxR= 65154.428709232
  Iteration  68: MaxR= 72269.163888256
  Iteration  69: MaxR= 22910.430641889
  Iteration  70: MaxR= 38200.165495889
  Iteration  71: MaxR= 40247.119924750
  Iteration  72: MaxR= 16309.351208125
  Iteration  73: MaxR= 42273.522483131
  Iteration  74: MaxR= 37699.628191031
  Iteration  75: MaxR= 19502.864242305
  Iteration  76: MaxR= 23407.748458374
  Iteration  77: MaxR= 13122.063326792
  Iteration  78: MaxR= 26667.933179710
  Iteration  79: MaxR= 13238.092055261
  Iteration  80: MaxR= 33374.316622515
  Iteration  81: MaxR= 12830.184968274
  Iteration  82: MaxR= 15041.658335082
  Iteration  83: MaxR= 37538.977331472
  Iteration  84: MaxR= 13996.547092034
  Iteration  85: MaxR= 82069.491122623
  Iteration  86: MaxR= 23103.737689788
  Iteration  87: MaxR= 12378.893798329
  Iteration  88: MaxR= 25160.789201093
  Iteration  89: MaxR= 19546.708234463
  Iteration  90: MaxR= 11536.340845988
  Iteration  91: MaxR= 15664.458217734
  Iteration  92: MaxR= 18428.205833014
  Iteration  93: MaxR= 19762.149207520
  Iteration  94: MaxR= 12123.689676833
  Iteration  95: MaxR= 39232.759221762
  Iteration  96: MaxR= 22571.975604622
  Iteration  97: MaxR= 11539.591694477
  Iteration  98: MaxR= 12658.328495951
  Iteration  99: MaxR= 14094.238601767
  Iteration 100: MaxR= 31183.448937142
  Iteration 101: MaxR= 18682.387272796
  Iteration 102: MaxR= 15652.448673644
  Iteration 103: MaxR= 27106.784357117
  Iteration 104: MaxR= 14548.329935870
  Iteration 105: MaxR= 9854.008316190
  Iteration 106: MaxR= 32427.298118259
  Iteration 107: MaxR= 21713.654627297
  Iteration 108: MaxR= 16472.441157915
  Iteration 109: MaxR= 23291.778092284
  Iteration 110: MaxR= 26090.943565370
  Iteration 111: MaxR= 38922.937045268
  Iteration 112: MaxR= 41783.114783142
  Iteration 113: MaxR= 20533.006042995
  Iteration 114: MaxR= 37804.609501937
  Iteration 115: MaxR= 31931.377115376
  Iteration 116: MaxR= 24766.719084911
  Iteration 117: MaxR= 18181.508720229
  Iteration 118: MaxR= 30162.092418013
  Iteration 119: MaxR= 20960.731970629
  Iteration 120: MaxR= 25478.495869405
  Iteration 121: MaxR= 15839.076844656
  Iteration 122: MaxR= 24515.702248390
  Iteration 123: MaxR= 22338.705857240
  Iteration 124: MaxR= 28857.814040501
  Iteration 125: MaxR= 24260.850576603
  Iteration 126: MaxR= 29161.654787005
  Iteration 127: MaxR= 19444.617813793

下面这个是刚开始计算的：
Solving the CP-SCF equations (RIJCOSX)          ...
----------------------------------------------
IBatch 1 (of 16)
  Iteration 0: MaxR=  0.348067860
  Iteration 1: MaxR=  0.271028646
  Iteration 2: MaxR=  0.021010919
  Iteration 3: MaxR=  0.011627070
  Iteration 4: MaxR=  0.006768669
  Iteration 5: MaxR=  0.002707154
  Iteration 6: MaxR=  0.001430541
  Iteration 7: MaxR=  0.000521569
  Iteration 8: MaxR=  0.000187784
  Iteration 9: MaxR=  0.000090435
  Iteration  10: MaxR=  0.000035761
  Iteration  11: MaxR=  0.000011801
  Iteration  12: MaxR=  0.000005530
  Iteration  13: MaxR=  0.000001724
  Iteration  14: MaxR=  0.000000807
  Iteration  15: MaxR=  0.000000362
  Iteration  16: MaxR=  0.000000145
  Iteration  17: MaxR=  0.000000069
  Iteration  18: MaxR=  0.000000030
  Iteration  19: MaxR=  0.000000012
  Iteration  20: MaxR=  0.000000006

作者
Author: sobereva 时间: 2016-6-12 22:36
DFT要精确算Hessian需要解CPSCF方程来得到波函数对坐标的导数。CPSCF本身和SCF一样也是要迭代求解的。
一开始出现那个说明CPSCF顺利收敛得到了Hessian，而最后那个，则是CPSCF不收敛。orca里算频率时CPSCF不收敛几率不小。

不管CPSCF是否能收敛得到Hessian和频率，由于当前几何优化都没收敛，说这个也没什么意义，算出来频率也白搭。应当先把几何优化搞收敛。

作者
Author: dingliping1108 时间: 2016-6-13 09:20

sobereva 发表于 2016-6-12 22:36
DFT要精确算Hessian需要解CPSCF方程来得到波函数对坐标的导数。CPSCF本身和SCF一样也是要迭代求解的。
一 ...

谢谢sob老师，那我是不是应该把优化最后一步得到的构型拿出来再继续优化？

作者
Author: sobereva 时间: 2016-6-13 09:34

dingliping1108 发表于 2016-6-13 09:20
谢谢sob老师，那我是不是应该把优化最后一步得到的构型拿出来再继续优化？

是
但也可能是震荡了之类，根据具体情况解决，光是这么做未必奏效

作者
Author: dingliping1108 时间: 2016-6-13 15:18

sobereva 发表于 2016-6-13 09:34
是
但也可能是震荡了之类，根据具体情况解决，光是这么做未必奏效

谢谢sob老师

欢迎光临计算化学公社 (http://bbs.keinsci.com/)