Dear all,
Based on the manual p.60 (section 4.8.3 *DIPOLEMOMENTMATRIX),
the u_ii denotes the permanent dipole moment for the i'th excited state, that is, <iui>
However, the source code or comments of output shows that
u_ii comes from the transition dipole moments between state X and Y : <X  A  <A>  Y>,
when X=Y, <X  A  <A>  Y> = <XAY>  <XY><A> = <XAY>  Detla_XY *<GAG> = <XAX>  <GAG>, G means ground state
that is, u_ii seems to be the difference between the dipole moments of excited state X and gound state G.
So, I want to make sure what the u_ii means.
Any help will be appreciated.
Best regards.
Lan
Question about output of the full dipole moment matrix

 Posts: 7
 Joined: 27 Aug 2013, 17:34
 First name(s): Nanna
 Middle name(s): Holmgaard
 Last name(s): List
Re: Question about output of the full dipole moment matrix
Dear Lan,
The u_ii is the difference between the expectation values of the position operator of the excited state and the ground state (the minus in the dipole operator is not included). I.e.
 u_ii = <XAX>  <GAG>, where A is the dipole operator.
To compute the dipole moment of the excited states, you therefore also need the ground state dipole moment from a .RUN PROPERTIES calculation. (Alternatively, if you use .RUN RESPONSE, only the electronic part of the dipole moment to the ground state will be computed and you will need to add the nuclear contribution by hand).
Best regards,
Nanna
The u_ii is the difference between the expectation values of the position operator of the excited state and the ground state (the minus in the dipole operator is not included). I.e.
 u_ii = <XAX>  <GAG>, where A is the dipole operator.
To compute the dipole moment of the excited states, you therefore also need the ground state dipole moment from a .RUN PROPERTIES calculation. (Alternatively, if you use .RUN RESPONSE, only the electronic part of the dipole moment to the ground state will be computed and you will need to add the nuclear contribution by hand).
Best regards,
Nanna

 Posts: 74
 Joined: 11 Nov 2013, 00:36
 First name(s): Youzhao
 Last name(s): Lan
 Affiliation: Institute of Physical Chemistry
 Country: China
Re: Question about output of the full dipole moment matrix
Dear Nanna,
Thanks for your reply. I am sorry for not enough information in the orginal post.
I am now using LSDalton 2015 which can provide the full dipole moment matrix.
As an example, in the following output of H2O molecule with the first four excited states:
full output please see attachment
HERE, I want to know what diagonal elements (X,X) X!=0 is in this Full Dipole Moment Matrix.
Are they the dipole moments of excited states or the differences between dipole moments i.e., <XAX>  <GAG>, as shown in the preceding output
for example: (1,1)_x =0.50302310 in the full dipole moment matrix
and in the preceding output
The transition dipole moments between state X and Y for operator XDIPLEN: <X  A  <A>  Y>
Column 1 Column 2 Column 3 Column 4
1 0.50302310 0.00000000 1.15779947 0.00000000
2 0.00000000 0.55086143 0.00000000 1.13501285
Best regards.
Lan
Thanks for your reply. I am sorry for not enough information in the orginal post.
I am now using LSDalton 2015 which can provide the full dipole moment matrix.
As an example, in the following output of H2O molecule with the first four excited states:
full output please see attachment
Code: Select all
DipoleMomentMatrix: Transition moments between the groundstate and the excited states
STATE Freq(au) Freq(eV) X Y Z
1 0.290634 7.908566 0.0000000 0.0000000 0.1601016
2 0.362426 9.862112 0.3135477 0.4436653 0.0000000
3 0.371324 10.104248 0.0000000 0.0000000 0.0000023
4 0.457017 12.436052 0.4411302 0.3117509 0.0000000
The transition dipole moments between state X and Y for operator XDIPLEN: <X  A  <A>  Y>
Column 1 Column 2 Column 3 Column 4
1 0.50302310 0.00000000 1.15779947 0.00000000
2 0.00000000 0.55086143 0.00000000 1.13501285
3 1.15779947 0.00000000 0.42914374 0.00000000
4 0.00000000 1.13501285 0.00000000 0.51353763
The transition dipole moments between state X and Y for operator YDIPLEN: <X  A  <A>  Y>
.......................
The transition dipole moments between state X and Y for operator ZDIPLEN: <X  A  <A>  Y>
......................
The Full Dipole Moment Matrix
Column 0 indicate the Ground State. Element (0,0) is therefore the ground state dipole moment
Elements (0,X) is therefore the transition state dipole moment of the X. excited state
Elements (X,Y) is the transition dipole moment between state X and Y
Dipole Moment Matrix for X coordinate
Column 0  Column 1 Column 2 Column 3
0 0.49700610  0.00000000 0.31354766 0.00000000

1 0.00000000  0.50302310 0.00000000 1.15779947
2 0.31354766  0.00000000 0.55086143 0.00000000
3 0.00000000  1.15779947 0.00000000 0.42914374
4 0.44113018  0.00000000 1.13501285 0.00000000
Column 4
0 0.44113018

1 0.00000000
2 1.13501285
3 0.00000000
4 0.51353763
Dipole Moment Matrix for Y coordinate
.............
Dipole Moment Matrix for Z coordinate
..................
Are they the dipole moments of excited states or the differences between dipole moments i.e., <XAX>  <GAG>, as shown in the preceding output
for example: (1,1)_x =0.50302310 in the full dipole moment matrix
and in the preceding output
The transition dipole moments between state X and Y for operator XDIPLEN: <X  A  <A>  Y>
Column 1 Column 2 Column 3 Column 4
1 0.50302310 0.00000000 1.15779947 0.00000000
2 0.00000000 0.55086143 0.00000000 1.13501285
Best regards.
Lan
 Attachments

 H2Olsr.out
 (77.37 KiB) Downloaded 314 times
Re: Question about output of the full dipole moment matrix
They are the differences between dipole moments i.e., <XAX>  <GAG>, as shown in the preceding output
The only thing I did was collecting these informations. Naturally I could have subtracted the groundstate dipole moment but I did not. I did not think about it. Would you prefer if I change this?
TK
The only thing I did was collecting these informations. Naturally I could have subtracted the groundstate dipole moment but I did not. I did not think about it. Would you prefer if I change this?
TK

 Posts: 74
 Joined: 11 Nov 2013, 00:36
 First name(s): Youzhao
 Last name(s): Lan
 Affiliation: Institute of Physical Chemistry
 Country: China
Re: Question about output of the full dipole moment matrix
Dear tkjaer,
Thanks for your reply.
I recommend to add a line comment: (X,X) X!=0, denotes <XAX>  <GAG>
in the following comments for the full dipole moment matrix
Because the Element (0,0) would be zero, if all the diagonal elements are understood to be <XAX>  <GAG>
Best regards.
Lan
Thanks for your reply.
I can deal with it if I know its meaning.Would you prefer if I change this?
I recommend to add a line comment: (X,X) X!=0, denotes <XAX>  <GAG>
in the following comments for the full dipole moment matrix
Code: Select all
Column 0 indicate the Ground State. Element (0,0) is therefore the ground state dipole moment
Elements (0,X) is therefore the transition state dipole moment of the X. excited state
Elements (X,Y) is the transition dipole moment between state X and Y
Best regards.
Lan
Re: Question about output of the full dipole moment matrix
Comment have been added, and will be included in the next tarball/patch

 Posts: 8
 Joined: 20 Nov 2018, 01:56
 First name(s): Terri
 Middle name(s): Christine
 Last name(s): Lovell
 Affiliation: University of Oregon
 Country: United States
Re: Question about output of the full dipole moment matrix
I would like to clarify how to read the output of the full dipole moment matrix. I would like to know the change in permanent dipole moment between my ground and 1st excited state and ground and 2nd excited state (ie ∣Δµ01∣ and ∣Δµ02∣). To find this, do I figure out the square root of the sum of squares of my X, Y, and Z component for [1,1] in the transition dipole moment matrices (which would be µ11). Then the absolute value of µ11 minus the permanent dipole moment for the ground state (which is already given) would be the ∣Δµ01∣ I’m looking for? I’ve attached my output file and spread sheet to see if I’m doing things correctly.
Thank you!
Thank you!
 Attachments

 8cpp Transition and Permanent dipole moment calculations.xlsx
 (11.5 KiB) Downloaded 28 times

 8cppdipole_8cpp.out
 (137.37 KiB) Downloaded 27 times
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