计算化学公社

标题: 计算电场下激发态关键词写法问题求助 [打印本页]

作者
Author: 446584935 时间: 2021-12-19 12:38
标题: 计算电场下激发态关键词写法问题求助
本帖最后由 446584935 于 2021-12-19 18:18 编辑

各位老师们好!我想计算电场对链烃激发能的影响，对比了不加电场和Y方向0.001a.u.电场的链烃激发能的结果，输入关键词如下：
不加电场：  PBE1PBE/6-311g(d,p) TD(nstates=10) TD=full
加电场： PBE1PBE/6-311g(d,p) TD(nstates=10) nosymm field=read TD=full  末尾电场格式 0.000 0.001 0.000
输出文的激发能带电场的上万eV,十分不合理，请问各位老师是什么问题，该怎么解决呢？

不加电场输出文件
Excitation energies and oscillator strengths:
Excited State 1:    Singlet-A    8.6315 eV  143.64 nm  f=0.0000  <S**2>=0.000
   42 -> 51       0.11727
   49 -> 50       0.66666
   49 -> 52       -0.16318
This state for optimization and/or second-order correction.
Total Energy, E(CIS/TDA) =  -472.169792156
Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2:    Singlet-A    8.8423 eV  140.22 nm  f=0.0048  <S**2>=0.000
   42 -> 50       0.19590
   44 -> 50       0.12267
   49 -> 51       0.63865
   49 -> 55       -0.13922

Excited State 3:    Singlet-A    9.0685 eV  136.72 nm  f=0.0000  <S**2>=0.000
   42 -> 51       0.19137
   44 -> 51       0.14595
   49 -> 50       0.11635
   49 -> 52       0.63395

Excited State 4:    Singlet-A    9.1140 eV  136.04 nm  f=0.0001  <S**2>=0.000
   43 -> 52       0.13538
   46 -> 51       0.33324
   47 -> 51       -0.18171
   48 -> 50       0.50528
   49 -> 53       -0.23917

Excited State 5:    Singlet-A    9.1145 eV  136.03 nm  f=0.0000  <S**2>=0.000
   46 -> 50       -0.10680
   46 -> 52       -0.11278
   47 -> 50       0.56441
   47 -> 52       -0.22242
   48 -> 51       -0.28741

Excited State 6:    Singlet-A    9.1244 eV  135.88 nm  f=0.0000  <S**2>=0.000
   42 -> 56       -0.10176
   46 -> 51       0.12133
   48 -> 50       0.18103
   49 -> 53       0.64419

Excited State 7:    Singlet-A    9.1568 eV  135.40 nm  f=0.0000  <S**2>=0.000
   43 -> 51       0.22209
   46 -> 50       0.46901
   46 -> 52       0.12371
   47 -> 50       0.20252
   47 -> 52       -0.18689
   48 -> 51       0.34034

Excited State 8:    Singlet-A    9.2523 eV  134.00 nm  f=0.0022  <S**2>=0.000
   49 -> 54       0.65333
   49 -> 55       -0.21986

Excited State 9:    Singlet-A    9.2695 eV  133.75 nm  f=0.0006  <S**2>=0.000
   40 -> 51       0.13971
   43 -> 50       0.43751
   46 -> 51       0.33955
   47 -> 51       0.17480
   47 -> 55       -0.14327
   48 -> 50       -0.12534
   48 -> 52       0.28662

Excited State  10:    Singlet-A    9.3557 eV  132.52 nm  f=0.0256  <S**2>=0.000
   42 -> 52       0.17823
   44 -> 52       0.16265
   49 -> 51       0.10925
   49 -> 54       0.18723
   49 -> 55       0.59165
SavETr:  write IOETrn= 770 NScale= 10 NData=  16 NLR=1 NState= 10 LETran=    190.

加电场输出文件
Excitation energies and oscillator strengths:
Excited state symmetry could not be determined.
Excited State 1:    Singlet-?Sym  55489.3958 eV 0.02 nm  f=39.9310  <S**2>=0.000
   49 -> 50       0.70711
This state for optimization and/or second-order correction.
Total Energy, E(CIS/TDA) =  -61480358.4368
Copying the excited state density for this state as the 1-particle RhoCI density.

Excited state symmetry could not be determined.
Excited State 2:    Singlet-?Sym  69215.8351 eV 0.02 nm  f=67.4350  <S**2>=0.000
   49 -> 51       0.70711

Excited state symmetry could not be determined.
Excited State 3:    Singlet-?Sym  122610.0109 eV 0.01 nm  f=125.4801  <S**2>=0.000
   48 -> 50       0.70711

Excited state symmetry could not be determined.
Excited State 4:    Singlet-?Sym  136334.2497 eV 0.01 nm  f=61.2965  <S**2>=0.000
   48 -> 51       0.70711

Excited state symmetry could not be determined.
Excited State 5:    Singlet-?Sym  144367.6701 eV 0.01 nm  f=0.2642  <S**2>=0.000
   49 -> 52       0.70711

Excited state symmetry could not be determined.
Excited State 6:    Singlet-?Sym  147000.2137 eV 0.01 nm  f=0.2563  <S**2>=0.000
   49 -> 53       0.70711

Excited state symmetry could not be determined.
Excited State 7:    Singlet-?Sym  192252.2024 eV 0.01 nm  f=2.1834  <S**2>=0.000
   49 -> 54       0.70711

Excited state symmetry could not be determined.
Excited State 8:    Singlet-?Sym  209578.4368 eV 0.01 nm  f=2.1037  <S**2>=0.000
   47 -> 50       0.70711

Excited state symmetry could not be determined.
Excited State 9:    Singlet-?Sym  211489.5368 eV 0.01 nm  f=2.1228  <S**2>=0.000
   48 -> 52       0.70711

Excited state symmetry could not be determined.
Excited State  10:    Singlet-?Sym  214120.9573 eV 0.01 nm  f=0.4047  <S**2>=0.000
   48 -> 53       0.70711
SavETr:  write IOETrn= 770 NScale= 10 NData=  16 NLR=1 NState= 10 LETran=    190.

作者
Author: wzkchem5 时间: 2021-12-19 16:36
把前线轨道作个图，看看轨道形状是否合理

作者
Author: 446584935 时间: 2021-12-19 17:27

wzkchem5 发表于 2021-12-19 16:36
把前线轨道作个图，看看轨道形状是否合理

我对比了加电场和没加电场的HOMO 和LUMO的波函数图，没发现有很大的差异。
此外在我测试的过程中发现，我在没加电场的输入文件输入field=read的关键词但实际没有加入电场，输出的激发能的值也会是几万eV，我把field=read删除后就是正常的，所以猜测是不是算激发态的任务加电场的关键词写的有问题？

作者
Author: sobereva 时间: 2021-12-19 18:12
直接上传带电场的情况的gjf和out文件，否则体系特征、格式写没写对都无从判断

作者
Author: 446584935 时间: 2021-12-19 18:18

sobereva 发表于 2021-12-19 18:12
直接上传带电场的情况的gjf和out文件，否则体系特征、格式写没写对都无从判断

感谢老师回复，已经上传

作者
Author: sobereva 时间: 2021-12-19 18:20

446584935 发表于 2021-12-19 18:18
感谢老师回复，已经上传

把连接关系都删了
否则电场读的是连接关系部分的信息，显然实际加的电场数值离谱

仔细看输出文件里的信息：

The following finite field(s) will be applied:
An electric field of 1.0000 2.0000 1.0000

作者
Author: 446584935 时间: 2021-12-19 18:50

sobereva 发表于 2021-12-19 18:20
把连接关系都删了
否则电场读的是连接关系部分的信息，显然实际加的电场数值离谱

感谢老师！已经解决了！

欢迎光临计算化学公社 (http://bbs.keinsci.com/)