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标题: Dalton计算旋轨耦合矩阵元得到的X,Y,Z三个方向的跃迁偶极矩的单位如何换算成cm-1？ [打印本页]
作者
Author: catenarygong    时间: 2018-12-17 20:47
标题: Dalton计算旋轨耦合矩阵元得到的X,Y,Z三个方向的跃迁偶极矩的单位如何换算成cm-1？
输入文件如下：
  1. **DALTON INPUT
  2. .RUN RESPONS
  3. **WAVE FUNCTIONS
  4. .DFT
  5. B3LYP
  6. **INTEGRALS
  7. .MNF-SO
  8. **SCF INPUT
  9. .DOUBLY OCCUPIED
  10. **RESPONS
  11. *QUADRATIC
  12. .DOUBLE RESIDUE
  13. .ISPABC
  14. 1 0 1
  15. .PROPRT
  16. X1MNF-SO
  17. .PROPRT
  18. Y1MNF-SO
  19. .PROPRT
  20. Z1MNF-SO
  21. .ROOTS
  22. 3
  23. **END OF DALTON INPUT
复制代码
输出文件有关SOC的地方如下：
  1. @ Transition moment <B | A - <A> | C> in a.u. for
  2. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  3. @ B excited state no., symmetry, spin:             1    1    0
  4. @ C excited state no., symmetry, spin:             1    1    1

  6. @ B and C excitation energies, moment:   0.01880548   0.01041747  -0.00003987


  9. @ Transition moment <B | A - <A> | C> in a.u. for
  10. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  11. @ B excited state no., symmetry, spin:             1    1    0
  12. @ C excited state no., symmetry, spin:             1    1    1

  14. @ B and C excitation energies, moment:   0.01880548   0.01041747  -0.00002613


  17. @ Transition moment <B | A - <A> | C> in a.u. for
  18. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  19. @ B excited state no., symmetry, spin:             1    1    0
  20. @ C excited state no., symmetry, spin:             1    1    1

  22. @ B and C excitation energies, moment:   0.01880548   0.01041747   0.00011714


  25. @ Transition moment <B | A - <A> | C> in a.u. for
  26. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  27. @ B excited state no., symmetry, spin:             2    1    0
  28. @ C excited state no., symmetry, spin:             1    1    1

  30. @ B and C excitation energies, moment:   0.03088657   0.01041747   0.00003424


  33. @ Transition moment <B | A - <A> | C> in a.u. for
  34. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  35. @ B excited state no., symmetry, spin:             2    1    0
  36. @ C excited state no., symmetry, spin:             1    1    1

  38. @ B and C excitation energies, moment:   0.03088657   0.01041747  -0.00003202


  41. @ Transition moment <B | A - <A> | C> in a.u. for
  42. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  43. @ B excited state no., symmetry, spin:             2    1    0
  44. @ C excited state no., symmetry, spin:             1    1    1

  46. @ B and C excitation energies, moment:   0.03088657   0.01041747   0.00008007


  49. @ Transition moment <B | A - <A> | C> in a.u. for
  50. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  51. @ B excited state no., symmetry, spin:             3    1    0
  52. @ C excited state no., symmetry, spin:             1    1    1

  54. @ B and C excitation energies, moment:   0.04062704   0.01041747  -0.00078376


  57. @ Transition moment <B | A - <A> | C> in a.u. for
  58. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  59. @ B excited state no., symmetry, spin:             3    1    0
  60. @ C excited state no., symmetry, spin:             1    1    1

  62. @ B and C excitation energies, moment:   0.04062704   0.01041747   0.00019726


  65. @ Transition moment <B | A - <A> | C> in a.u. for
  66. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  67. @ B excited state no., symmetry, spin:             3    1    0
  68. @ C excited state no., symmetry, spin:             1    1    1

  70. @ B and C excitation energies, moment:   0.04062704   0.01041747  -0.00084584


  73. @ Transition moment <B | A - <A> | C> in a.u. for
  74. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  75. @ B excited state no., symmetry, spin:             1    1    0
  76. @ C excited state no., symmetry, spin:             2    1    1

  78. @ B and C excitation energies, moment:   0.01880548   0.01714880   0.00000259


  81. @ Transition moment <B | A - <A> | C> in a.u. for
  82. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  83. @ B excited state no., symmetry, spin:             1    1    0
  84. @ C excited state no., symmetry, spin:             2    1    1

  86. @ B and C excitation energies, moment:   0.01880548   0.01714880  -0.00000077


  89. @ Transition moment <B | A - <A> | C> in a.u. for
  90. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  91. @ B excited state no., symmetry, spin:             1    1    0
  92. @ C excited state no., symmetry, spin:             2    1    1

  94. @ B and C excitation energies, moment:   0.01880548   0.01714880  -0.00001531


  97. @ Transition moment <B | A - <A> | C> in a.u. for
  98. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  99. @ B excited state no., symmetry, spin:             2    1    0
  100. @ C excited state no., symmetry, spin:             2    1    1

  102. @ B and C excitation energies, moment:   0.03088657   0.01714880  -0.00031241


  105. @ Transition moment <B | A - <A> | C> in a.u. for
  106. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  107. @ B excited state no., symmetry, spin:             2    1    0
  108. @ C excited state no., symmetry, spin:             2    1    1

  110. @ B and C excitation energies, moment:   0.03088657   0.01714880   0.00031985


  113. @ Transition moment <B | A - <A> | C> in a.u. for
  114. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  115. @ B excited state no., symmetry, spin:             2    1    0
  116. @ C excited state no., symmetry, spin:             2    1    1

  118. @ B and C excitation energies, moment:   0.03088657   0.01714880  -0.00068080


  121. @ Transition moment <B | A - <A> | C> in a.u. for
  122. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  123. @ B excited state no., symmetry, spin:             3    1    0
  124. @ C excited state no., symmetry, spin:             2    1    1

  126. @ B and C excitation energies, moment:   0.04062704   0.01714880  -0.00000260


  129. @ Transition moment <B | A - <A> | C> in a.u. for
  130. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  131. @ B excited state no., symmetry, spin:             3    1    0
  132. @ C excited state no., symmetry, spin:             2    1    1

  134. @ B and C excitation energies, moment:   0.04062704   0.01714880  -0.00000349


  137. @ Transition moment <B | A - <A> | C> in a.u. for
  138. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  139. @ B excited state no., symmetry, spin:             3    1    0
  140. @ C excited state no., symmetry, spin:             2    1    1

  142. @ B and C excitation energies, moment:   0.04062704   0.01714880  -0.00002406


  145. @ Transition moment <B | A - <A> | C> in a.u. for
  146. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  147. @ B excited state no., symmetry, spin:             1    1    0
  148. @ C excited state no., symmetry, spin:             3    1    1

  150. @ B and C excitation energies, moment:   0.01880548   0.03054659   0.00002935


  153. @ Transition moment <B | A - <A> | C> in a.u. for
  154. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  155. @ B excited state no., symmetry, spin:             1    1    0
  156. @ C excited state no., symmetry, spin:             3    1    1

  158. @ B and C excitation energies, moment:   0.01880548   0.03054659   0.00003380


  161. @ Transition moment <B | A - <A> | C> in a.u. for
  162. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  163. @ B excited state no., symmetry, spin:             1    1    0
  164. @ C excited state no., symmetry, spin:             3    1    1

  166. @ B and C excitation energies, moment:   0.01880548   0.03054659   0.00002814


  169. @ Transition moment <B | A - <A> | C> in a.u. for
  170. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  171. @ B excited state no., symmetry, spin:             2    1    0
  172. @ C excited state no., symmetry, spin:             3    1    1

  174. @ B and C excitation energies, moment:   0.03088657   0.03054659  -0.00000965


  177. @ Transition moment <B | A - <A> | C> in a.u. for
  178. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  179. @ B excited state no., symmetry, spin:             2    1    0
  180. @ C excited state no., symmetry, spin:             3    1    1

  182. @ B and C excitation energies, moment:   0.03088657   0.03054659   0.00000406


  185. @ Transition moment <B | A - <A> | C> in a.u. for
  186. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  187. @ B excited state no., symmetry, spin:             2    1    0
  188. @ C excited state no., symmetry, spin:             3    1    1

  190. @ B and C excitation energies, moment:   0.03088657   0.03054659  -0.00001460


  193. @ Transition moment <B | A - <A> | C> in a.u. for
  194. @ A operator label,    symmetry, spin:      X1MNF-SO    1    1
  195. @ B excited state no., symmetry, spin:             3    1    0
  196. @ C excited state no., symmetry, spin:             3    1    1

  198. @ B and C excitation energies, moment:   0.04062704   0.03054659   0.00023718


  201. @ Transition moment <B | A - <A> | C> in a.u. for
  202. @ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
  203. @ B excited state no., symmetry, spin:             3    1    0
  204. @ C excited state no., symmetry, spin:             3    1    1

  206. @ B and C excitation energies, moment:   0.04062704   0.03054659   0.00017156


  209. @ Transition moment <B | A - <A> | C> in a.u. for
  210. @ A operator label,    symmetry, spin:      Z1MNF-SO    1    1
  211. @ B excited state no., symmetry, spin:             3    1    0
  212. @ C excited state no., symmetry, spin:             3    1    1

  214. @ B and C excitation energies, moment:   0.04062704   0.03054659  -0.00076484
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抱歉问如此低级的问题
最近才开始初学这部分的计算
一直认为跃迁偶极矩的单位是a.u.到debye这样的转换，但是很多文献里给的<Sn|HSO|Tn>的单位是cm-1....
我尝试用Hartree到wavenumber这样的转换，但是感觉不太对
作者
Author: abin    时间: 2018-12-17 23:33
@ Transition moment <B | A - <A> | C> in a.u. for
@ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
@ B excited state no., symmetry, spin:             3    1    0
@ C excited state no., symmetry, spin:             1    1    1

@ B and C excitation energies, moment:   0.04062704   0.01041747   0.00019726
这里大概说，
S3 energy = 0.04062704 au
T1 energy = 0.01041747
使用MNF-SO方案，Y方向， 考虑single electron SO情形下，得到的SOCME大概是0.00019726 au = 43.293565514 cm^-1.
同理可以得到其他方向的分量。

然后使用下面的方式求解：
<S3 | SOC | T1 > = sqrt(x **2 + y ** 2 + z ** 2)

如果计算得到的数据很离谱，那么请仔细阅读Dalton手册（你可能使用错了基组）。
作者
Author: 小范范1989    时间: 2018-12-18 08:24
abin 发表于 2018-12-17 23:33
@ Transition moment  in a.u. for
@ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
@  ...

你好，请问一下，基组对SOC的计算也有影响？
比如说6-31g*和3-21g*计算出来的差距会很大？没测试过，所以来问问，谢谢指点
作者
Author: 小范范1989    时间: 2018-12-18 08:24
1a.u.=2.1947*10^5 cm-1
作者
Author: abin    时间: 2018-12-18 13:07
小范范1989 发表于 2018-12-18 08:24
你好，请问一下，基组对SOC的计算也有影响？
比如说6-31g*和3-21g*计算出来的差距会很大？没测试过，所 ...

手册有讲到，
MNF-SO应该需要使用全电子基组， 并且最好是手册里指定的基组类别。
这个手册有讲到的。

用其他的基组，得到的结果是否可靠， 不晓得。

我只是follow了手册， 别的情况没有测试。
作者
Author: 小范范1989    时间: 2018-12-19 08:36
abin 发表于 2018-12-18 13:07
手册有讲到，
MNF-SO应该需要使用全电子基组， 并且最好是手册里指定的基组类别。
这个手册有讲到的 ...

谢谢指点。
作者
Author: blueyangliu    时间: 2018-12-19 09:21
abin 发表于 2018-12-18 13:07
手册有讲到，
MNF-SO应该需要使用全电子基组， 并且最好是手册里指定的基组类别。
这个手册有讲到的 ...

那岂不是过渡金属没法用这个方法算了
作者
Author: abin    时间: 2018-12-19 09:32
blueyangliu 发表于 2018-12-19 09:21
那岂不是过渡金属没法用这个方法算了

不了解， 不做判定。

自己根据手册理解哦。

In the present implementation, the mean-field approach works only for basis sets with a generalized contraction scheme such as the ANO basis sets, raf-r, or cc-pVXZ(-DK). For other types of basis sets, the program might work without a crash, but it will most likely provide erroneous results.

以上是手册原文。
自行理解哦。
作者
Author: rabbit0602    时间: 2022-4-9 10:13
abin 发表于 2018-12-17 23:33
@ Transition moment  in a.u. for
@ A operator label,    symmetry, spin:      Y1MNF-SO    1    1
@  ...

您好 请问SOC的计算 不需要在根号里除以3吗？
作者
Author: 喵星大佬    时间: 2022-4-9 10:38
你从哪里看出来要除以3的
作者
Author: rabbit0602    时间: 2022-4-9 11:05
喵星大佬 发表于 2022-4-9 10:38
你从哪里看出来要除以3的

https://pubs.rsc.org/en/content/ ... 858e/unauth#tab2fna
您好 我看的是这篇文献 后半部分table2中hso的计算公式
作者
Author: abin    时间: 2022-4-9 14:15
rabbit0602 发表于 2022-4-9 10:13
您好 请问SOC的计算 不需要在根号里除以3吗？

自己根据手册理解哦。

In the present implementation, the mean-field approach works only for basis sets with a generalized contraction scheme such as the ANO basis sets, raf-r, or cc-pVXZ(-DK). For other types of basis sets, the program might work without a crash, but it will most likely provide erroneous results.

以上是手册原文。
自行理解哦。

手册中的相似位置，
还有关于ECP基组的描述呢。

我记得Dalton 论坛有讲，
使用ECP基组处理SOCME 纯粹是瞎扯淡。
作者
Author: guodx    时间: 2023-8-6 00:57
请问楼主的输入文件用的是哪个态的结构算的SOC
作者
Author: zjxitcc    时间: 2023-8-6 09:57
guodx 发表于 2023-8-6 00:57
请问楼主的输入文件用的是哪个态的结构算的SOC

无需问楼主。wzkchem5大神在本论坛上回答过大量关于SOC的帖子，用必应或谷歌随便搜一下，就可以看到。建议把这些帖子里wzkchem5的回复全都看一遍。




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