two photon- DOUBLE RESIDUE

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Zeljka.San
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two photon- DOUBLE RESIDUE

Post by Zeljka.San » 01 Jul 2014, 11:01

Hi, everybody,

I have to calculate TPA cross section, and I have been using:
**RESPONSE
*QUADRATIC
.TWO-PHOTON
.ROOTS
20

which gives me TPA cross section. But this method sometimes gives unreasonable values for TPA, so I want to calculate TPA using .DOUBLE RESIDUE keyword but I cannot get TPA cross section.
I get excited to excited states dipole moments using just .DOUBLE RESIDUE, but I want to continue calculation to get also TPA cross section (as in paper J. Chem. Theory Comput., 2010, 6 (9), pp 2809–2821, http://pubs.acs.org/doi/abs/10.1021/ct1 ... istoryKey=)
Please, could anyone tell me what aditional keyword I have to use?
Thanks!
Zeljka

kennethruud
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Re: two photon- DOUBLE RESIDUE

Post by kennethruud » 01 Jul 2014, 16:05

Dalton will, using the .DOUBLE RESIDUE keyword, only provide you with the excited-state to excited-state transition moments. The evaluation of the TPA cross sections, you will have to do on your own, using this data. In this process, you will also have to select how many excited states you want to include in the sum-over-states expression for the TPA cross section, compare Eq. (2) of the paper you refer to.


Best regards,

Kenneth

Kenneth Ruud
Prorector of Research, UiT - The Arctic University of Norway
Telephone: +47 77623101
http://www.ctcc.no/people/senior-scient ... index.html

Zeljka.San
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Re: two photon- DOUBLE RESIDUE

Post by Zeljka.San » 02 Jul 2014, 07:13

Thank you for clarification!
Greetings,
Željka

rizzo
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Re: two photon- DOUBLE RESIDUE

Post by rizzo » 02 Jul 2014, 09:21

Dear Zeljca

I would love to know what you mean by "It gives unreasonable values for TPA".
I see no reasons why that should happen IF all the parameters of the calculation
(basi set, structure model, all the other input parameters) are reasonable. Short of
a possible bug in the program, of which I am not aware at this stage.

Thanks and

best regards

Antonio Rizzo

kennethruud
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Re: two photon- DOUBLE RESIDUE

Post by kennethruud » 02 Jul 2014, 10:15

Antonio,

This can happen if you have systems with nearly degenerate intermediate states, so that you get divergencies in the response function, not uncommon if you have molecules with some symmetry. It is of course also a way to experimentally boost TPA cross sections.


Best regards,

Kenneth

Zeljka.San
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Re: two photon- DOUBLE RESIDUE

Post by Zeljka.San » 02 Jul 2014, 10:40

Dear Antonio,

Prof. Ruud answered your question. Precisely, I have system with symmetry D2h.
Closed in attachement is paper in which is stated that this problem can be solved used .DOUBLE RESIDUE and damping factor GAMMA, even if we would program this by ourselves and connect SOS with excited to excited state transition moments and TPA we need to know the work using GAMMA damping factors. We would be very grateful if you would let us know on the literature on damping factors. Moreover, let us know if you are familiar with the programs connection SOS and TPA calculations because it wold save us time.
Thank you and best regards,
Željka
Attachments
Day_Nguyen_Pachter_2010 .pdf
(1.04 MiB) Downloaded 223 times

rizzo
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Re: two photon- DOUBLE RESIDUE

Post by rizzo » 02 Jul 2014, 17:36

Thanks Kenneth, and thanks Zeljka

indeed as you say, Kenneth, that is a case where lowest order perturbation theory fails, and therefore it is
simply a case that should be treated with a non perturbative approach, or with inclusion of the proper higher
order terms in the perturbation... The solution is not to use the method, which indeed, as such, is giving the
only result it can give...

Sorry then, I was really worried by the sentence "this method sometimes gives unreasonable values for TPA",
because the use of DALTON for calculations of TPA cross sections is more and more common (see the number of
publications in the literature) and it is important to know that we are not bumping into something that configures
as a "bug".... ;-)

Best regards

Antonio

taylor
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Re: two photon- DOUBLE RESIDUE

Post by taylor » 12 Jul 2014, 05:32

I have debated with myself for some time about buying in to a discussion in which both Kenneth and Antonio have given complete and very helpful answers to your question. However, my concern is with your question itself, and I feel compelled to at least say something.

In your input fragment you appear to be asking for 20 roots in the response calculation. I would assert that it is simply an illusion to think that any calculation that is likely to be feasible can give a useful description of 20 excited states! As I have posted both on this forum and its predecessor mailing list before (many times...) it is inconceivable that in the spectrum of excited states, 20+ of them will be dominated by single excitations from the ground state. And those that are not dominated by single excitations will require a treatment (from a Dalton perspective, MCSCF response or CC response) that can properly describe the multiconfigurational nature of those excited states. Even then, for an MCSCF treatment one would have to constantly review and perhaps (to check) extend the active space to ensure it was capable of describing the excited states in a response calculation, and in the CC case possibly use as high a level as CC3 to be \emph{sure} the excited states can be adequately described. If you are using a single-reference method such as SCF or DFT response, then it is almost certainly the case that a number of your 20 roots are completely unphysical. I have posted before about the (actual: the molecule is s-tetrazine) situation in which DFT response places the lowest 1Ag state at more than double the experimental excitation energy --- the problem is that this state, which is in experiment one of the lowest excited states, is in reality dominated by a double excitation from the ground state, and single-reference response misses this completely.

In addition, in a neutral molecule, it is also very unlikely indeed that in the lowest 20 states there is not at least one or more states that are dominantly Rydberg in character. Most of these can actually be reasonably well described by single-reference response methods, \emph{but} they will only be placed correctly in the calculated spectrum (in fact, may only appear even at all in the spectrum) when the basis set used for the calculation is properly augmented with the necessary diffuse functions to describe such states.

You say your molecule actually has D2h symmetry, in which case (see other postings of mine on the forum about using symmetry) I am surprised you run without symmetry: you are likely using an order of magnitude more CPU time than is actually needed. But the presence of symmetry does not in any way diminish the force of what I said above (and my favourite s-tetrazine example in fact has D2h symmetry and as I said it is the lowest singlet state in symmetry 1 that is a problem). If you want to trust the results of calculations of 20 excited states, you will need to do a great deal of analysis and calibration calculations to verify they are being meaningfully described. Otherwise you are building a house on sand, I'm afraid.

I hope this comment is taken as an attempt to be helpful: I am not motivated by a desire to criticize, more by a desire to see the program used well and in a way that makes a genuine contribution in a particular area.

Best regards
Pete

Zeljka.San
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Re: two photon- DOUBLE RESIDUE

Post by Zeljka.San » 14 Jul 2014, 11:20

Dear Pete,
thank you for your comment, I am glad you enrolled in discussion. I am aware of the limits of the DFT theory, I am testing DALTON input, and output and I do not trust the calculation for high excited states.
Thanks again!
Best regards,
Zeljka

Addiw7
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Re: two photon- DOUBLE RESIDUE

Post by Addiw7 » 16 Apr 2017, 11:48

Dear All,

Could you point what I am missing in my input so that I get the error at the end of attached output file, please?
DALTON_MOLECULE.out
(92.11 KiB) Downloaded 21 times

kennethruud
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Re: two photon- DOUBLE RESIDUE

Post by kennethruud » 16 Apr 2017, 11:53

Replace ".DOUBLE RESIDUE" with ".TWO-PHOTON" and things should work fine (the two-photon transition moment is a single residue of the quadratic response function), see Chapter 11 in the Dalton manual. (I assume the title of your posting is correct, and that you are not looking for the excited-state dipole moment, which is given as a double residue of the quadratic response function).

Kenneth

Addiw7
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Re: two photon- DOUBLE RESIDUE

Post by Addiw7 » 16 Apr 2017, 14:01

No, professor Ruud, I want to calculate transition moments between excited-states.

kennethruud
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Re: two photon- DOUBLE RESIDUE

Post by kennethruud » 16 Apr 2017, 14:35

Somewhat misleading title of your post. Anyway, try adding the keyword .DIPLEN after **QUADRATIC, assuming you want the transition dipole moments between excited states.

*QUADRATIC
.DOUBLE RESIDUE
.DIPLEN
.ROOTS
5

This will provide you with the necessary electric dipole operators needed to calculate the transition moment.


Best regards,

Kenneth

Addiw7
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Re: two photon- DOUBLE RESIDUE

Post by Addiw7 » 19 Apr 2017, 09:23

Thank you. I got what I wanted.

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