为什么加了派电子布居数增加，轨道贡献并没有发生变化

ddddnight · 发表于 Post on 2023-7-7 23:38:57

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

sobereva · 发表于 Post on 2023-7-8 09:50:39

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。

ddddnight · 发表于 Post on 2023-7-8 11:36:02

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

sobereva · 发表于 Post on 2023-7-9 10:26:34

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。

ddddnight · 发表于 Post on 2023-7-9 13:12:22

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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[波函数分析求助] 为什么加了派电子布居数增加，轨道贡献并没有发生变化