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标题: 关于Multiwfn空穴电子分析结果与实验结果对比分析问题 [打印本页]

作者
Author: seantan521 时间: 2018-11-26 21:31
标题: 关于Multiwfn空穴电子分析结果与实验结果对比分析问题
大家好，我最近算了几个Donor-Acceptor-Donor材料的Hole/Electron分布，结果发现有几个地方和实验得到的数据似乎不太相符，请问该怎么解释？

本次计算：
第一部分gaussian计算，是以优化过的S0极小点为基础，优化S1得到的激发态数据；
第二部分multiwfn计算，是以优化过的S1结构，计算energy，并分析S1的空穴电子分布（P3额外分析了S3,因为S3的f比S1和S2大得多）。

P1,P2,P3 acceptor一样，donor逐渐减弱，三者结构很类似。
实验结果是，从P1到P3，UV,PL出现明显蓝移，S1,T1,ΔEst都逐步增大，PLQY增大。
UV,PL蓝移和S1,T1增大，和计算结果非常一致。ΔEst逐步增大和gaussian结果也一致。但是PLQY不知道怎么分析了。

我根据计算结果是这样分析的：P1和P2的S1应该是HLCT state，Sm/Sr增大，说明LE成分增强，所以PLQY增大；D，|μ|，H_CT，H减小，Δσ，t增大，说明CT成分减弱，所以ΔEst增大。
但是对于P3,不知道应该按照S1还是S3分析。如果按照S3分析，确实Sm/Sr增大，LE成分增强，所以PLQY增大；但S3应该是比较明显的LE state，但是实际上属于CT才有的溶剂化效应也很明显。如果按照S1分析，Sm/Sr减小，LE成分减弱，所以PLQY应该最小才对，其他数据也看不出什么规律来。

数据有点多，但愿我表达没太多毛病，还望大家给出指导意见来，谢谢了！

以下是以优化过的S0极小点为基础，优化S1得到的数据：
P1:

Excited State 1:    Singlet-A    2.5624 eV  483.85 nm  f=0.3599  <S**2>=0.000
   191 -> 192       0.68666
   191 -> 193    -0.11760
This state for optimization and/or second-order correction.
Total Energy, E(TD-HF/TD-DFT) =  -2657.31263326
Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2:    Singlet-A    2.7818 eV  445.70 nm  f=0.2121  <S**2>=0.000
   190 -> 192    -0.68952
   190 -> 193    -0.11363

Excited State 3:    Singlet-A    3.1230 eV  397.01 nm  f=0.0064  <S**2>=0.000
   191 -> 192    -0.13481
   191 -> 193    -0.61634
   191 -> 194    -0.28345

P2:

Excited State 1:    Singlet-A    2.7212 eV  455.62 nm  f=0.2723  <S**2>=0.000
   159 ->160       -0.69017
   159 ->161       0.10574
This state for optimization and/or second-order correction.
Total Energy, E(TD-HF/TD-DFT) =  -2880.80836576
Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2:    Singlet-A    3.2197 eV  385.08 nm  f=0.1575  <S**2>=0.000
   158 ->160       0.68866
   158 ->161       0.13791

Excited State 3:    Singlet-A    3.3786 eV  366.97 nm  f=0.0080  <S**2>=0.000
   159 ->160       -0.12676
   159 ->161       -0.66740
   159 ->162       -0.12771
   159 ->163       -0.10657

P3:

Excited State 1:    Singlet-A    3.0590 eV  405.31 nm  f=0.0218  <S**2>=0.000
   167 ->168       -0.69929
This state for optimization and/or second-order correction.
Total Energy, E(TD-HF/TD-DFT) =  -2320.30706947
Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2:    Singlet-A    3.3841 eV  366.37 nm  f=0.0493  <S**2>=0.000
   166 ->168       0.69856

Excited State 3:    Singlet-A    3.7836 eV  327.69 nm  f=1.0347  <S**2>=0.000
   165 ->168       0.69092

为节省大家时间，空穴电子分析的相关数据列在此处了，详细数据也列在了帖子末尾处。

	Sm	Sr	D	\|μ\|	Δσ	H_CT	H	t	Excitation energy
	a.u.	a.u.	A	a.u.	A	A	A	A	eV
P1-S1	0.2757	0.55236	5.458	10.300901	0.506	3.48	4.532	1.977	2.562
P2-S1	0.28381	0.56828	5.009	9.451717	1.225	2.574	3.778	2.435	2.721
P3-S1	0.17731	0.37369	6.213	11.743834	0.907	2.228	3.216	3.985	3.059
P3-S3	0.4966	0.75775	1.97	3.721192	-1.648	4.07	4.955	-2.1	3.784

Integral of hole:       0.998287
Integral of electron: 0.999194
Integral of transition density: -0.000932
Transition dipole moment in X/Y/Z:  -2.267361  -0.782868  -0.052416 a.u.
Sm index (integral of Sm function): 0.27570 a.u.
Sr index (integral of Sr function): 0.55236 a.u.
Centroid of hole in X/Y/Z:    -6.815602 -0.745754 -0.754003 Angstrom
Centroid of electron in X/Y/Z: -2.132248 1.946587 0.024413 Angstrom
D_x: 4.683  D_y: 2.692  D_z: 0.778 D index: 5.458 Angstrom
Variation of dipole moment with respect to ground state:
X: -8.839106  Y: -5.081376  Z: -1.469140 Norm: 10.300901 a.u.
RMSD of hole in X/Y/Z:    3.730 1.552 1.410 Norm: 4.279 Angstrom
RMSD of electron in X/Y/Z: 4.079 2.194 1.199 Norm: 4.785 Angstrom
Difference between RMSD of hole and electron (delta sigma):
X:  0.349  Y:  0.643  Z: -0.211 Overall:  0.506 Angstrom
H_x:  3.904  H_y:  1.873  H_z:  1.305  H_CT:  3.480  H index:  4.532 Angstrom
t index:  1.977 Angstrom
Ghost-hunter index (def 1):    5.606 eV, 1st/2nd terms:  8.245    2.638 eV
Ghost-hunter index (def 2):    4.201 eV, 1st/2nd terms:  6.839    2.638 eV
Excitation energy of this state:    2.562 eV
Note: Probably this is a ghost state, because excitation energy is lower than ghost-hunter index of definition 2

Integral of hole:       0.997560
Integral of electron: 0.999599
Integral of transition density: 0.001032
Transition dipole moment in X/Y/Z: 1.753251  -0.970181 0.078687 a.u.
Sm index (integral of Sm function): 0.28381 a.u.
Sr index (integral of Sr function): 0.56828 a.u.
Centroid of hole in X/Y/Z:       7.108670 -1.739129 0.264028 Angstrom
Centroid of electron in X/Y/Z: 3.114258 1.279441 0.407102 Angstrom
D_x: 3.994  D_y: 3.019  D_z: 0.143 D index: 5.009 Angstrom
Variation of dipole moment with respect to ground state:
X: 7.537622  Y: -5.696166  Z: -0.269987 Norm: 9.451717 a.u.
RMSD of hole in X/Y/Z:    2.148 1.779 1.497 Norm: 3.166 Angstrom
RMSD of electron in X/Y/Z: 3.536 2.264 1.283 Norm: 4.391 Angstrom
Difference between RMSD of hole and electron (delta sigma):
X:  1.388  Y:  0.485  Z: -0.214 Overall:  1.225 Angstrom
H_x:  2.842  H_y:  2.022  H_z:  1.390  H_CT:  2.574  H index:  3.778 Angstrom
t index:  2.435 Angstrom
Ghost-hunter index (def 1):    6.274 eV, 1st/2nd terms:  9.149    2.875 eV
Ghost-hunter index (def 2):    4.855 eV, 1st/2nd terms:  7.730    2.875 eV
Excitation energy of this state:    2.721 eV
Note: Probably this is a ghost state, because excitation energy is lower than ghost-hunter index of definition 2

Integral of hole:       1.000992
Integral of electron: 0.999419
Integral of transition density: 0.000122
Transition dipole moment in X/Y/Z:  -0.365779  -0.174894  -0.355876 a.u.
Sm index (integral of Sm function): 0.17731 a.u.
Sr index (integral of Sr function): 0.37369 a.u.
Centroid of hole in X/Y/Z:    -8.262085 -1.782182 0.835192 Angstrom
Centroid of electron in X/Y/Z: -3.143385 1.567431 -0.252927 Angstrom
D_x: 5.119  D_y: 3.350  D_z: 1.088 D index: 6.213 Angstrom
Variation of dipole moment with respect to ground state:
X: -9.674930  Y: -6.331152  Z: 2.056669 Norm: 11.743834 a.u.
RMSD of hole in X/Y/Z:    1.975 1.399 1.332 Norm: 2.762 Angstrom
RMSD of electron in X/Y/Z: 2.976 1.834 1.115 Norm: 3.669 Angstrom
Difference between RMSD of hole and electron (delta sigma):
X:  1.001  Y:  0.435  Z: -0.217 Overall:  0.907 Angstrom
H_x:  2.476  H_y:  1.616  H_z:  1.223  H_CT:  2.228  H index:  3.216 Angstrom
t index:  3.985 Angstrom
Ghost-hunter index (def 1):    5.754 eV, 1st/2nd terms:  8.072    2.318 eV
Ghost-hunter index (def 2):    5.857 eV, 1st/2nd terms:  8.174    2.318 eV
Excitation energy of this state:    3.059 eV
Note: Probably this is a ghost state, because excitation energy is lower than ghost-hunter index of definition 2

Integral of hole:       1.000119
Integral of electron: 0.999456
Integral of transition density: 0.000314
Transition dipole moment in X/Y/Z:  -3.277050  -0.644315  -0.082948 a.u.
Sm index (integral of Sm function): 0.49660 a.u.
Sr index (integral of Sr function): 0.75775 a.u.
Centroid of hole in X/Y/Z:    -0.281679 0.900260 -0.096908 Angstrom
Centroid of electron in X/Y/Z: -2.056340 1.746909 -0.211110 Angstrom
D_x: 1.775  D_y: 0.847  D_z: 0.114 D index: 1.970 Angstrom
Variation of dipole moment with respect to ground state:
X: 3.352911  Y: -1.599596  Z: 0.215765 Norm: 3.721192 a.u.
RMSD of hole in X/Y/Z:    5.308 2.030 1.053 Norm: 5.779 Angstrom
RMSD of electron in X/Y/Z: 3.536 1.819 1.117 Norm: 4.131 Angstrom
Difference between RMSD of hole and electron (delta sigma):
X: -1.771  Y: -0.211  Z:  0.064 Overall: -1.648 Angstrom
H_x:  4.422  H_y:  1.925  H_z:  1.085  H_CT:  4.070  H index:  4.955 Angstrom
t index: -2.100 Angstrom
Ghost-hunter index (def 1):    1.803 eV, 1st/2nd terms:  9.114    7.311 eV
Ghost-hunter index (def 2):    1.506 eV, 1st/2nd terms:  8.817    7.311 eV
Excitation energy of this state:    3.784 eV

作者
Author: ggdh 时间: 2018-11-26 21:57
用s1,一般不要违背kasha规则
PLQY不光和重叠有关，还和gap，分子柔性，isc等有关，一般gap大，IC小，会导致QY大
所以在解释实验现象的时候，没必要强行用sr去解释qy

作者
Author: seantan521 时间: 2018-11-26 22:10

ggdh 发表于 2018-11-26 21:57
用s1,一般不要违背kasha规则
PLQY不光和重叠有关，还和gap，分子柔性，isc等有关，一般gap大，IC小，会导 ...

嗯嗯，因为三个结构其实很类似，感觉分子柔性差距不会很大，但是因为削弱了共轭，gap确实变大了，从这里解释PLQY增大确实可行。
那么，在正式文章中，怎么解释S3的振子强度远大于S1,S2，以及P3的空穴电子重叠最少，但PLQY最大这个事实？因为，只要把数据挂出来总觉得怪怪的。

作者
Author: seantan521 时间: 2018-11-27 21:04

ggdh 发表于 2018-11-26 21:57
用s1,一般不要违背kasha规则
PLQY不光和重叠有关，还和gap，分子柔性，isc等有关，一般gap大，IC小，会导 ...

还是有些不知道怎么解释。
比如说我这个系列设计了6种结构，对比发现，不管是分析电荷效应还是空间效应，只要我削弱了共轭，都得到了明显的蓝移，但是一般削弱共轭造成的蓝移和减色效应是一块出现的，但我的偏偏结果表明，随着我削弱共轭，PLQY在不断升高。
对于gap大，IC小，PLQY大，我也有个疑问。如果三个激发态都参与了吸收，而由于S3的f比较大，所以更多的吸收发生在S3。这时，如果gap比较小，那么是不是更容易通过VR和IC转换到S1，从而产生更大的PLQY呢？

作者
Author: seantan521 时间: 2018-11-27 21:08
恳求卢老师能否解释一下，这个问题困扰好久了。如果几个激发态都参与了吸收或者激发，如何判断他们对PLQY的贡献？@Sobereva

作者
Author: ggdh 时间: 2018-11-29 10:39
本帖最后由 ggdh 于 2018-11-29 10:45 编辑

seantan521 发表于 2018-11-27 21:04
还是有些不知道怎么解释。
比如说我这个系列设计了6种结构，对比发现，不管是分析电荷效应还是空间效应 ...

IC 特指S1到S0的IC，S3到S1的IC由于速度太快基本不用考虑。对PLQY也没有影响
你前面所有的问题都是因为你没搞懂Kasha规则。
既然发射过程只跟S1相关，你管S2 S3干什么。PLQY也只跟S1的各种过程相关。
吸收发射不要弄混了。减色效应一般是用在吸收中，跟PLQY也没啥关系。

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