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标题: 为什么加了派电子布居数增加，轨道贡献并没有发生变化 [打印本页]
作者
Author: ddddnight    时间: 2023-7-7 23:38
标题: 为什么加了派电子布居数增加，轨道贡献并没有发生变化
本帖最后由 ddddnight 于 2023-7-8 11:33 编辑

对溴化环氧树脂沿着C1-Br29键加了电场和Fe的作用，算的mulliken pi电子布居数变多，但是NAdO方法算得Fe轨道贡献并没有发生太大变化呀
pi电子布居数的计算方法是
19  //轨道定域化
1  //对占据轨道做轨道定域化（非占据轨道对分析结果无贡献，故不用对非占据轨道也做定域化）
100  //主功能100
22  //检测pi轨道
-1  //当前内存里的轨道是定域化过的轨道
0  //开始检测pi轨道。用屏幕上的选项可以修改判断pi轨道的阈值，这里暂且不改
此时屏幕上提示了检测出的pi型LMO的编号，一共发现了7个，接着输入
2  //把其它轨道占据数清零
0  //回到主菜单
7  //布居分析
5  //Mulliken布居分析
1  //输出Mulliken布居数和原子电荷

  
Normal-π  electron population
  
Atom
1(C )
Population:
1.11817
Net charge
4.88183
Atom
2(C )
Population:
1.01357
Net  charge
4.98643
Atom
3(C )
Population:
0.92161
Net  charge
5.07839
Atom
4(C )
Population:
0.89365
Net  charge
5.10635
Atom
5(C )
Population:
1.32332
Net  charge
4.67668
Atom
6(C )
Population:
0.74352
Net  charge
5.25648
Atom
7(H )
Population:
-0.01236
Net  charge
1.01236
Atom
8(H )
Population:
0.0253
Net  charge
0.9747
Atom
9(C )
Population:
0.94681
Net  charge
5.05319
Atom
10(C )
Population:
0.92413
Net  charge
5.07587
Atom
11(C )
Population:
0.98223
Net  charge
5.01777
Atom
12(C )
Population:
1.30504
Net  charge
4.69496
Atom
13(H )
Population:
0.02711
Net  charge
0.97289
Atom
14(C )
Population:
1.33161
Net  charge
4.66839
Atom
15(H )
Population:
0.00672
Net  charge
0.99328
Atom
16(C )
Population:
0.49685
Net  charge
5.50315
Atom
17(C )
Population:
0.08131
Net  charge
5.91869
Atom
18(C )
Population:
0.03257
Net  charge
5.96743
Atom
19(H )
Population:
-4.88E-04
Net  charge
1.00049
Atom
20(H )
Population:
-0.01368
Net charge
1.01368
Atom
21(H )
Population:
-0.00294
Net  charge
1.00294
Atom
22(C )
Population:
0.01899
Net  charge
5.98101
Atom
23(H )
Population:
-0.00717
Net  charge
1.00717
Atom
24(H )
Population:
-0.00329
Net  charge
1.00329
Atom
25(H )
Population:
-9.88E-04
Net  charge
1.00099
Atom
26(O )
Population:
-0.01235
Net  charge
8.01235
Atom
27(O )
Population:
-0.00711
Net  charge
8.00711
Atom
28(Br)
Population:
3.94489
Net  charge
31.05511
Atom
29(Br)
Population:
1.9549
Net charge
33.0451
Atom
30(Br)
Population:
3.94905
Net  charge
31.05095
Atom
31(Br)
Population:
3.96195
Net  charge
31.03805
Atom
32(C )
Population:
0.01782
Net  charge
5.98218
Atom
33(H )
Population:
0.00245
Net  charge
0.99755
Atom
34(H )
Population:
0.00129
Net  charge
0.99871
Atom
35(H )
Population:
0.00127
Net  charge
0.99873
Atom
36(C )
Population:
0.01828
Net  charge
5.98172
Atom
37(H )
Population:
0.00411
Net  charge
0.99589
Atom
38(H )
Population:
0.00542
Net  charge
0.99458
Atom
39(H )
Population:
0.00642
Net  charge
0.99358
Under  electric filed -π electron population
Atom
1(C )
Population:
1.31916
Net charge
4.68084
Atom
2(C )
Population:
1.00749
Net charge
4.99251
Atom
3(C )
Population:
0.943
Net charge
5.057
Atom
4(C )
Population:
0.86673
Net charge
5.13327
Atom
5(C )
Population:
1.30781
Net charge
4.69219
Atom
6(C )
Population:
0.47854
Net charge
5.52146
Atom
7(H )
Population:
0.01104
Net charge
0.98896
Atom
8(H )
Population:
0.01909
Net charge
0.98091
Atom
9(C )
Population:
0.95447
Net charge
5.04553
Atom
10(C )
Population:
0.90823
Net charge
5.09177
Atom
11(C )
Population:
0.98365
Net charge
5.01635
Atom
12(C )
Population:
1.27947
Net charge
4.72053
Atom
13(H )
Population:
0.02533
Net charge
0.97467
Atom
14(C )
Population:
1.27403
Net charge
4.72597
Atom
15(H )
Population:
0.00238
Net charge
0.99762
Atom
16(C )
Population:
0.53345
Net charge
5.46655
Atom
17(C )
Population:
0.11107
Net charge
5.88893
Atom
18(C )
Population:
0.03426
Net charge
5.96574
Atom
19(H )
Population:
0.00545
Net charge
0.99455
Atom
20(H )
Population:
-0.01974
Net charge
1.01974
Atom
21(H )
Population:
-0.00541
Net charge
1.00541
Atom
22(C )
Population:
0.01009
Net charge
5.98991
Atom
23(H )
Population:
-0.01091
Net charge
1.01091
Atom
24(H )
Population:
-0.00304
Net charge
1.00304
Atom
25(H )
Population:
0.00569
Net charge
0.99431
Atom
26(O )
Population:
0.00266
Net charge
7.99734
Atom
27(O )
Population:
-3.483E-4
Net charge
8.00035
Atom
28(Br)
Population:
2.01529
Net charge
32.98471
Atom
29(Br)
Population:
3.92595
Net charge
31.07405
Atom
30(Br)
Population:
3.9473
Net charge
31.0527
Atom
31(Br)
Population:
2.01166
Net charge
32.98834
Atom
32(C )
Population:
0.00731
Net charge
5.99269
Atom
33(H )
Population:
0.00723
Net charge
0.99277
Atom
34(H )
Population:
0.00786
Net charge
0.99214
Atom
35(H )
Population:
0.00465
Net charge
0.99535
Atom
36(C )
Population:
0.01464
Net charge
5.98536
Atom
37(H )
Population:
0.00212
Net charge
0.99788
Atom
38(H )
Population:
0.00487
Net charge
0.99513
Atom
39(H )
Population:
0.00748
Net charge
0.99252

  
Eigenvalues  of NAdOs: (sum= 1.19001 )-Normal
  
0.86484
0.22094
0.1061
0.02547
0.00947

Eigenvalues of NAdOs: (sum= 1.19538 )-Under  electric filed
0.87953
0.24920
0.11447
0.02632
0.00837

Eigenvalues of NAdOs: (sum= 1.19215 )-Fe  catalyst
0.8677
0.22517
0.10711
0.02515
0.00906






作者
Author: sobereva    时间: 2023-7-8 09:50
别把pi写成派

提问也太省事了。连个体系结构图或者结构文件都没有，原子在什么位置都无从辨别。NAdO轨道图也不贴，别人都不知道各个本征值对应什么轨道。也不说清楚mulliken pi电子布居具体怎么算的。波函数文件也没有。
作者
Author: ddddnight    时间: 2023-7-8 11:36
sobereva 发表于 2023-7-8 09:50
别把pi写成派

提问也太省事了。连个体系结构图或者结构文件都没有，原子在什么位置都无从辨别。NAdO轨道 ...

好的老师，以后一定注意。今天重新算了一下，对数据进行了修改，对上面问题进行了修改，由于发帖长度不够，Fe的布居数表格放在这一层了，相关文件和NAdO轨道图片已经上传网盘。
链接：https://pan.baidu.com/s/1nlYvD7kH8NUIgTfUMzLBnA?pwd=ci22
提取码：ci22
  
Fe  catalyst-π electron population
  
Atom
1(C )
Population:
1.37098
Net charge
4.62902
Atom
2(C )
Population:
0.97809
Net charge
5.02191
Atom
3(C )
Population:
0.99409
Net charge
5.00591
Atom
4(C )
Population:
0.93029
Net charge
5.06971
Atom
5(C )
Population:
1.23741
Net charge
4.76259
Atom
6(C )
Population:
0.83098
Net charge
5.16902
Atom
7(H )
Population:
0.0078
Net charge
0.9922
Atom
8(H )
Population:
0.02193
Net charge
0.97807
Atom
9(C )
Population:
0.91268
Net charge
5.08732
Atom
10(C )
Population:
0.95818
Net charge
5.04182
Atom
11(C )
Population:
0.99002
Net charge
5.00998
Atom
12(C )
Population:
1.11068
Net charge
4.88932
Atom
13(H )
Population:
0.02271
Net charge
0.97729
Atom
14(C )
Population:
1.12714
Net charge
4.87286
Atom
15(H )
Population:
7.69E-04
Net charge
0.99923
Atom
16(C )
Population:
0.9128
Net charge
5.0872
Atom
17(C )
Population:
0.10026
Net charge
5.89974
Atom
18(C )
Population:
0.0196
Net charge
5.9804
Atom
19(H )
Population:
1.29E-04
Net charge
0.99987
Atom
20(H )
Population:
-0.01368
Net charge
1.01368
Atom
21(H )
Population:
-9.07E-04
Net charge
1.00091
Atom
22(C )
Population:
0.0195
Net charge
5.9805
Atom
23(H )
Population:
-0.00817
Net charge
1.00817
Atom
24(H )
Population:
-0.00112
Net charge
1.00112
Atom
25(H )
Population:
-0.00252
Net charge
1.00252
Atom
26(O )
Population:
0.00167
Net charge
7.99833
Atom
27(O )
Population:
1.68766
Net charge
6.31234
Atom
28(Br)
Population:
3.87708
Net charge
31.12292
Atom
29(Br)
Population:
5.92699
Net charge
29.07301
Atom
30(Br)
Population:
1.95061
Net charge
33.04939
Atom
31(Br)
Population:
1.95493
Net charge
33.04507
Atom
32(C )
Population:
0.137
Net charge
5.863
Atom
33(H )
Population:
-0.01453
Net charge
1.01453
Atom
34(H )
Population:
0.01404
Net charge
0.98596
Atom
35(H )
Population:
0.0191
Net charge
0.9809
Atom
36(C )
Population:
0.01705
Net charge
5.98295
Atom
37(H )
Population:
-2.76E-03
Net charge
1.00276
Atom
38(H )
Population:
-5.13E-04
Net charge
1.00051
Atom
39(H )
Population:
-0.00137
Net charge
1.00137
Atom
40(Fe)
Population:
5.91341
Net charge
20.08659


作者
Author: sobereva    时间: 2023-7-9 10:26
看这些太抽象。
我的建议是，加电场后先别优化结构，保持和原先坐标相同。然后用Multiwfn绘制加电场和不加电场之间的密度差图，看看C-Br附近电子密度怎么变化的，一下子就清楚了。至于键的强度有什么变化，Multiwfn算个Mayer键级便知。把Mayer的变化和密度差图结合试图分析，如果确实从图上看sigma或pi电子增多了、Mayer键级也加大了，再去通过Multiwfn用NAdO进一步对键级的变化内在原因细化。

先搞清楚结构不变的情况下电场会带来什么影响。在此之前不建议把结构变化的影响掺和进来，免得不好分析、说不清楚。

另外，有的Br的pi布居数达到3.9473，那肯定是把孤对电子也算进来了，如果只分析pi电子的话应该挨个看当前的占据轨道，把对应Br的孤对电子的轨道占据数用主功能6的子功能26清零。
作者
Author: ddddnight    时间: 2023-7-9 13:12
sobereva 发表于 2023-7-9 10:26
看这些太抽象。
我的建议是，加电场后先别优化结构，保持和原先坐标相同。然后用Multiwfn绘制加电场和不加 ...

了解了，谢谢老师的指导



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