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？

catenarygong · 发表于 Post on 2018-12-17 20:47:17

输入文件如下：

**DALTON INPUT
.RUN RESPONS
**WAVE FUNCTIONS
.DFT
B3LYP
**INTEGRALS
.MNF-SO
**SCF INPUT
.DOUBLY OCCUPIED
**RESPONS
*QUADRATIC
.DOUBLE RESIDUE
.ISPABC
1 0 1
.PROPRT
X1MNF-SO
.PROPRT
Y1MNF-SO
.PROPRT
Z1MNF-SO
.ROOTS
3
**END OF DALTON INPUT

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输出文件有关SOC的地方如下：

@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 1 1 1
@ B and C excitation energies, moment: 0.01880548 0.01041747 -0.00003987
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Y1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 1 1 1
@ B and C excitation energies, moment: 0.01880548 0.01041747 -0.00002613
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 1 1 1
@ B and C excitation energies, moment: 0.01880548 0.01041747 0.00011714
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 1 1 1
@ B and C excitation energies, moment: 0.03088657 0.01041747 0.00003424
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Y1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 1 1 1
@ B and C excitation energies, moment: 0.03088657 0.01041747 -0.00003202
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 1 1 1
@ B and C excitation energies, moment: 0.03088657 0.01041747 0.00008007
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-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 -0.00078376
@ Transition moment | 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
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-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 -0.00084584
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.01880548 0.01714880 0.00000259
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Y1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.01880548 0.01714880 -0.00000077
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.01880548 0.01714880 -0.00001531
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.03088657 0.01714880 -0.00031241
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Y1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.03088657 0.01714880 0.00031985
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.03088657 0.01714880 -0.00068080
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 3 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.04062704 0.01714880 -0.00000260
@ Transition moment | 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: 2 1 1
@ B and C excitation energies, moment: 0.04062704 0.01714880 -0.00000349
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 3 1 0
@ C excited state no., symmetry, spin: 2 1 1
@ B and C excitation energies, moment: 0.04062704 0.01714880 -0.00002406
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ B and C excitation energies, moment: 0.01880548 0.03054659 0.00002935
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Y1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ B and C excitation energies, moment: 0.01880548 0.03054659 0.00003380
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ B and C excitation energies, moment: 0.01880548 0.03054659 0.00002814
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ B and C excitation energies, moment: 0.03088657 0.03054659 -0.00000965
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Y1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ B and C excitation energies, moment: 0.03088657 0.03054659 0.00000406
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 2 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ B and C excitation energies, moment: 0.03088657 0.03054659 -0.00001460
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: X1MNF-SO 1 1
@ B excited state no., symmetry, spin: 3 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ B and C excitation energies, moment: 0.04062704 0.03054659 0.00023718
@ Transition moment | 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: 3 1 1
@ B and C excitation energies, moment: 0.04062704 0.03054659 0.00017156
@ Transition moment | C> in a.u. for
@ A operator label, symmetry, spin: Z1MNF-SO 1 1
@ B excited state no., symmetry, spin: 3 1 0
@ C excited state no., symmetry, spin: 3 1 1
@ 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

abin · 发表于 Post on 2018-12-17 23:33:18

@ Transition moment | 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）。

小范范1989 · 发表于 Post on 2018-12-18 08:24:01

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

小范范1989 · 发表于 Post on 2018-12-18 08:24:50

1a.u.=2.1947*10^5 cm-1

abin · 发表于 Post on 2018-12-18 13:07:04

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。

小范范1989 · 发表于 Post on 2018-12-19 08:36:47

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。

blueyangliu · 发表于 Post on 2018-12-19 09:21:04

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

abin · 发表于 Post on 2018-12-19 09:32:05

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。

rabbit0602 · 发表于 Post on 2022-4-9 10:13:25

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？

喵星大佬 · 发表于 Post on 2022-4-9 10:38:23

你从哪里看出来要除以3的

rabbit0602 · 发表于 Post on 2022-4-9 11:05:25

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

abin · 发表于 Post on 2022-4-9 14:15:39

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。

guodx · 发表于 Post on 2023-8-6 00:57:20

请问楼主的输入文件用的是哪个态的结构算的SOC

zjxitcc · 发表于 Post on 2023-8-6 09:57:14

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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[Dalton] 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？