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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
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发表于 Post on 2018-11-26 21:31:53
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