Quadratic response calculation

[eliezer]

Hello everyone,
I am starting to study the theoretical optical absorption of excited states of organic molecules. To do that, I need to learn how to calculate the quadratic response with double residues and I know that DALTON perform these type of calculation. I am trying to do some tests with DALTON, but I do not know if I am using the correct keywords. I am using the following ".dal" file (in the ".mol" file I inserted basis set and the cartesian coordinates of a structure optimized in excited state S1):

**GENERAL
.RUN RESPONSE
.DIRECT
*PARALLEL
**WAVE FUNCTION
.DFT
CAMB3LYP
**RESPONSE
*QUADRA
.DIPLEN
.DOUBLE RESIDUE
.ROOTS
5
*END OF

Is that input right or I need to put something more? In the output, where can I find the obtained excitations and contributions?

Someone could help me or give me some tips?

Thank you!

Quadratic response calculation with DALTON - ResearchGate. Available from: https://www.researchgate.net/post/Quadr ... ith_DALTON [accessed Apr 12, 2016].

[quartarolo]

Hi,
which kind of absorption spectra are you going to calculate, one- or two-photon electronic spectra?

domenico

[taylor]

Let me expand on Domenico's posting: what is it you want to do? Telling us you want to calculate quadratic response and asking us to say whether your input is correct is asking us to read your mind! (Unless there are obvious gross errors in your input.) It will be much easier for us to help --- and we are invariably willing to do so --- if you ask a specific question, not one that is so general there are dozens of answers! Also, have you looked through the test jobs to see whether there is anything related to what you want to do? There are very many possibilities among the test suite.

Best regards
Pete

[eliezer]

Let me expand on Domenico's posting: what is it you want to do? Telling us you want to calculate quadratic response and asking us to say whether your input is correct is asking us to read your mind! (Unless there are obvious gross errors in your input.) It will be much easier for us to help --- and we are invariably willing to do so --- if you ask a specific question, not one that is so general there are dozens of answers! Also, have you looked through the test jobs to see whether there is anything related to what you want to do? There are very many possibilities among the test suite.

Best regards
Pete

Hi,
which kind of absorption spectra are you going to calculate, one- or two-photon electronic spectra?

domenico

Sorry by not to be more specific in the question.

I want to study the one-photon absorption from excited states of some organic molecules, in order to evaluate the photo-physics from pump-probe experiment. Then, I know that I have to calculate the quadratic response with double residues in order to evaluate the possible transitions starting from the S1 (or other) excited state. As I am new user in DALTON, firstly I am trying to reproduce the results of one paper (J Phys Chem C, 2013, 117, 6889) and then, study the cases that I have interest. I did not find an example of this kind of calculation in the test jobs of DALTON

Studying the manual and some examples in the internet, I built the input above to do this calculate. But, I do not know if I insert the correct keywords in the input and where the information of the occurred electronic transitions (and the orbitals contribution) are shown in the output.

Overall, I want to calculate the allowed electronic transitions starting from a specific excited state (for example, S1->Sn). Then, I would like to know how to do this calculation and where I have to search the results in the output.

Best regards,
Eliezer

[sonco]

Hello,

your input looks fine if you run in C1 symmetry, otherwise you need to specify the number of roots per IRREP.
The relevant output looks like this

@Transition moment <B | A | C> in a.u. for
@A operator label, symmetry, spin: XDIPLEN 1 0
@B excited state no., symmetry, spin: 1 1 0
@C excited state no., symmetry, spin: 3 1 0

@B and C excitation energies, moment: 0.20156926 0.25149532 0.41168010 [<<<< this is it, with states B, C and the dipole comp. as given in the previous lines]

which should be relatively self-explanatory. Notice you'll also get "transitions" like <B | A | B > (so the exc state dipole moments)

Unless you want to do it by hand, my suggestion is to write a python script to do the post processing and find all the Sn->Sm
transition moments (and the Sm->Sn as well) and remove the <Sn|A|Sn> moments...

Give it a try and if you get in troubles write back to the forum
Best regards
Sonia

[eliezer]

Hello,

your input looks fine if you run in C1 symmetry, otherwise you need to specify the number of roots per IRREP.
The relevant output looks like this

@Transition moment <B | A | C> in a.u. for
@A operator label, symmetry, spin: XDIPLEN 1 0
@B excited state no., symmetry, spin: 1 1 0
@C excited state no., symmetry, spin: 3 1 0

@B and C excitation energies, moment: 0.20156926 0.25149532 0.41168010 [<<<< this is it, with states B, C and the dipole comp. as given in the previous lines]

which should be relatively self-explanatory. Notice you'll also get "transitions" like <B | A | B > (so the exc state dipole moments)

Unless you want to do it by hand, my suggestion is to write a python script to do the post processing and find all the Sn->Sm
transition moments (and the Sm->Sn as well) and remove the <Sn|A|Sn> moments...

Give it a try and if you get in troubles write back to the forum
Best regards
Sonia

Thank you Sonia, I will try!

Best regards
Eliezer

[hjaaj]

Just a short comment. In Dalton we have tried to always let the most important lines with results start with a '@' in column 1 (I am sure you can find important output where we haven't yet added an '@' in column 1, you are welcome to let us know if/when you find cases like that).

The idea is that you from the big Dalton output file can get a summary by doing the unix/linux command grep '@' my_dalton_calc.out > my_dalton_calc.summary.

[eliezer]

Just a short comment. In Dalton we have tried to always let the most important lines with results start with a '@' in column 1 (I am sure you can find important output where we haven't yet added an '@' in column 1, you are welcome to let us know if/when you find cases like that).

The idea is that you from the big Dalton output file can get a summary by doing the unix/linux command grep '@' my_dalton_calc.out > my_dalton_calc.summary.

Thank you by the information! I will pay attention in the "@" along the output.

Best regards,
Eliezer

[eliezer]

Dear all,
I did the calculation of allowed electronic transitions starting from S1 excited state, according to the input show above and with the suggestion of Dr. Sonia. I am getting some blocks like this:

--------------------------------------------------------------------------------------------------------------------
@ Transition moment <B | A - <A> | C> in a.u. for
@ A operator label, symmetry, spin: ZDIPLEN 1 0
@ B excited state no., symmetry, spin: 1 1 0
@ C excited state no., symmetry, spin: 2 1 0

@ B and C excitation energies, moment: 0.13170418 0.16733093 -0.21504440
--------------------------------------------------------------------------------------------------------------------

For this block example, am I having a transition S1->S2, right? Is the transition 0.03562675 a.u.?

I would need the orbital contributions in each allowed transition and the oscillator strength; do I need to insert some specific keywords to do this? I did not find in the output no information thereof (different when we perform linear response, in which this information is given in the output.

Thank you in advance
Eliezer

[olav]

This output means

E(S1) - E(S0) = 0.13170418
E(S2) - E(S0) = 0.16733093
<S1|z|S2> = -0.21504440

all in a.u.

Regards,
Olav

[sonco]

And yes, you'll compute the energy S2-S1 by difference [E(S2) - E(S0)]- [E(S1) - E(S0)]= 0.16733093-0.13170418=0.03562675 a.u.

Sonia

[quartarolo]

In order to have more information from the output file and in particular to know orbital contributions to the transitions, you need to add the keyword .PRINT LEVEL under *QUADRA section:
*QUADRA
.PRINT LEVEL
10
(the number set should be greater than two, the default. I don't know exactly which value is more appropriate for you)

[eliezer]

This output means

E(S1) - E(S0) = 0.13170418
E(S2) - E(S0) = 0.16733093
<S1|z|S2> = -0.21504440

all in a.u.

Regards,
Olav

And yes, you'll compute the energy S2-S1 by difference [E(S2) - E(S0)]- [E(S1) - E(S0)]= 0.16733093-0.13170418=0.03562675 a.u.

Sonia

In order to have more information from the output file and in particular to know orbital contributions to the transitions, you need to add the keyword .PRINT LEVEL under *QUADRA section:
*QUADRA
.PRINT LEVEL
10
(the number set should be greater than two, the default. I don't know exactly which value is more appropriate for you)

Thank you all, very kind of you! I will try now all these tips.

Sincerely,
Eliezer

[xiaolin wang]

Dear everyone
I want to calculate the transition dipole moment from T1 to ground state. I make a test (see attachment, the input file I do not upload are presented in output ), and I have no idea whether the output is correct. If I am worng, please help me. I hope to get your help. Thank you.


Best regards
xiaolin

[olav]

It is not correct since the S0-T1 transition dipole moment is spin-forbidden. What your input describes is <S|r*s_z|T>. What you probably want is the higher-order phosphorescence transition. Look in the test cases for *phosph* to see an example

Olav

[xiaolin wang]

Dear Olav
Thank you very much for your quick reply. I want to compute the transition dipole moments of Sn-Tn and S0-T1 rather than phosphorescence transition. First, I calculate the transition dipole moment of Sn-Tn according to posts, but I do not know whether the output is correct. If it's convenient for you, could you help me look at the output file is right? (see attachment) Second, I recently read the literature (Journal of Materials Chemistry C, 2016, 4 6829-6838), the TableS3 list the transition dipole moments of molecule from T1 to S0. I also want to calculate this dipole moment, but I don't know what example should I refer to or what key word should I add ? I need your help and hope to get your help. Thank you.

Best regards
xiaolin

[olav]

The dipole transition Sn-Tn is still spin forbidden and you need a perturbation such as spin-orbit to get a non-zero value, i.e. this is a phosphorescence transition. In Dalton you can only do this with S0-Tn (quadratic response single residue) where S0 is the reference ground state. It is not possible to calculate this for the more general case Sn-Tn.

Olav

[taylor]

Olav has already solved your problem for you, although of course learning that there is no mechanism for computing spin-forbidden matrix elements between Sn and Tn may not be the answer you had hoped for. But let me add one thing. If your molecule(s) of interest has some spatial symmetry then it may be that you can perform e.g. an MCSCF calculation on an excited singlet that is the lowest state of its given symmetry. In the most extreme case (that Dalton can handle) of D2h symmetry you could specify up to eight states of different spatial symmetry as "S0" and then do the phosphoresence transitions, as Olav has outlined. Obviously, if your molecule has no symmetry this is not helpful, but just in case...

Best regards
Pete

[xiaolin wang]

Dear olav and taylor
Thank you very much for your advisements. I read seriously the advisements, and I make a test (see attachment). Dear olav, I add the .ECPHOS ( my molecule contain the heavy metal atom with ecp basis ) keyword under *QUADRATIC after I read ‘ this is a phosphorescence transition’. I do not know whether I am correct. If I am wrong, please correct me. I don't know how to get the triplet state in this calculation, add the TRPFLG word or other word? The input shows in the following. I think I need a keyword from what I want. I will appreciate if I can get your help. Dear taylor, thank you for your kind. My molecule belong to C1 point group.
**DALTON INPUT
.RUN RESPONS
.DIRECT
**WAVE FUNCTIONS
.DFT
B3LYP
**RESPONS
*QUADRATIC
.SINGLE RESIDUE
.DIPLEN
.ECPHOS
.ROOTS
1
**END OF DALTON INPUT
Second order moment in a.u. for
A operator label, symmetry, spin: XDIPLEN 1 0
B operator label, symmetry, spin: X1SPNSCA 1 1
Excited state no., symmetry, spin: 1 1 1

omega B, excitation energy, moment : 0.000000 0.097103 0.037115


Second order moment in a.u. for
A operator label, symmetry, spin: YDIPLEN 1 0
B operator label, symmetry, spin: X1SPNSCA 1 1
Excited state no., symmetry, spin: 1 1 1

omega B, excitation energy, moment : 0.000000 0.097103 -0.019574


Second order moment in a.u. for
A operator label, symmetry, spin: ZDIPLEN 1 0
B operator label, symmetry, spin: X1SPNSCA 1 1
Excited state no., symmetry, spin: 1 1 1

omega B, excitation energy, moment : 0.000000 0.097103 -0.002109

I get three directions dipole of X1SPNSCA Y1SPNSCA and Z1SPNSCA, respectively. I have no idea whether the output is correct. I hope to get your help. Thank you.
Best regards
xiaolin

[olav]

The input is correct, but you can remove the DIPLEN keyword which will calculate a lot of things you do not need. The output is probably correct given the approximation that has been specified, but if it any good is for you to decide.

Regards,
Olav

[xiaolin wang]

Dear olav
Thank you very much for your kind and help. I have made a calculation that is computing. I have another question to ask you. I also want to calculate the transition dipole moment from S0 to Sn state. I know this calculation need QUADRATIC response with SINGLE RESIDUE, but my result (see attachment) seems to be wrong by adding the DIPLEN word under QUADRATIC. I think whether need to add another keyword to get what I want. I don’t know what to do. Any help is appreciated. Thank you. The input show in following.
**DALTON INPUT
.RUN RESPONS
.DIRECT
**WAVE FUNCTIONS
.DFT
B3LYP
**RESPONS
.MAXRM
500
*QUADRATIC
.DIPLEN
.SINGLE RESIDUE
.ROOTS
5
**END OF DALTON INPUT

Best regards
xiaolin

[xiaolin wang]

Dear olav and all
I found that I was wrong in terms of calculating the dipole moment from ground state to singlet excited states. I use the linear response with single residue to calculate the dipole moment of S0-Sn, and add the .DIPLEN under *LINEAR. I get a little bit of a deviation from the literature( (Journal of Materials Chemistry C, 2016, 4 6829-6838). I don't know whether I'm right. If I am wrong, could you tell me? At the same time, by setting the different values of ROOTS (5,10 see attachment), the result
I get have a little difference. I don't know what effect this difference has on the outcome. I need your help and hope to get your help. I will apperiate If I get your help. Thank you.

Best regards
xiaolin