SOS computation of dipole hyperpolarizabilities

MARMARA · 2019-07-05 18:50:08

In some molecules (especially those with high NLO responses) there is one dominant component that defines the magnitudes of either beta or gama. Is it possible In the current version of SOS method implemented in Multiwfn, to show the variation (convergence) of each tensor component of alpha beta and gamma with the number of excited states?
If not, this would be a very useful added feature for this methodology.
Cheers.

sobereva · 2019-07-06 15:07:13

Today I updated the Multiwfn 3.7(dev) on the Multiwfn website, please download and have a try. In this new version, after using option 6/7/16/17 of sum-over-states module of Multiwfn (subfunction 8 of main function 200), variation of all components of beta/gamma with respect to number of considered states / external frequency will be exported to a text file with _comp suffix in current folder.

I hope this update will be helpful for you.

MARMARA · 2019-07-08 09:37:09

Dear Tian,
thank you very much for the quick response. I tried the new modification and it seems that it works great. After this change we are able to study the convergence of each beta or gama component and easily define the excited state(s) delivering the largest contribution.
This is an important feature for a better understanding of the underlying mechanism.
Best
PK

MARMARA · 2019-07-09 11:07:49

Dear Tian, I have one more request (if this is possible).
The SOS equation for gamma has two terms gama^I and gama^II. Each of these terms give important information about the nature of the molecular second hyperpolarizability. For instance, in some molecules of large positive hyperpolarizabilities gama^II should be either small , or much smaller than gama^I. For systems with negative second order NLO responses (this is a very rear case but extremely interesting) gama^II should be the dominant one. If your code could print separately the evolution of gama^I and gama^II with respect to the number of states included in the sum FOR EACH TENSORIAL COMPONENT we could get enlightening information to be used in our analysis and also it would help those that want to design molecules of high second hyperpolarizabilities.

Last edited by MARMARA (2019-07-10 09:42:43)

sobereva · 2019-07-23 06:15:48

MARMARA wrote:

Dear Tian, I have one more request (if this is possible).
The SOS equation for gamma has two terms gama^I and gama^II. Each of these terms give important information about the nature of the molecular second hyperpolarizability. For instance, in some molecules of large positive hyperpolarizabilities gama^II should be either small , or much smaller than gama^I. For systems with negative second order NLO responses (this is a very rear case but extremely interesting) gama^II should be the dominant one. If your code could print separately the evolution of gama^I and gama^II with respect to the number of states included in the sum FOR EACH TENSORIAL COMPONENT we could get enlightening information to be used in our analysis and also it would help those that want to design molecules of high second hyperpolarizabilities.

I am sorry for omitting your this question, I just see this post. I will implement this soon and let you know.

sobereva · 2019-07-24 19:55:35

I have updated Multiwfn 3.7(dev) on the official website, in this version, when calculating variation of gamma with respect to frequency or number of considered states, all components of gamma I and gamma II will also be outputted as .txt file (e.g. gamma_II_n_comp.txt), please carefully check prompts on screen.

MARMARA · 2019-08-06 17:51:18

Very grateful about our help Haven't tested yet but I will do it soon enough and I will send you the feedback .!

cvalverde · 2020-06-08 10:36:27

I used the following input to calculate the SOS:

#p td=(nstates=150,root=1) IOp(9/40=5) scrf=(iefpcm, solvent=dmso) Int
=UltraFine scf=(xqc,maxcycle=5000) cam-b3lyp/6-311+G(d) polar=gamma PO
P=CHELPG density=current NoSymm

but in the calculation multiwfn is using the following information:
e.g. C: \ lovelive \ sunshine \ yosoro.out
Hint: If pressing ENTER button directly, the file with identical name as input file but with .out or .log suffix will be loaded
This file is recognized as a Gaussian output file
There are 1050 excited states, loading basic information ...

Loading configuration coefficients ...
Summary of excited states:

Is it okay to use 1050?

sobereva · 2020-06-08 11:10:28

"polar" keyword should never be used together with "TD", otherwise the output will be meaningless.

cvalverde · 2020-06-08 11:26:30

Which command to use to calculate gamma?

sobereva · 2020-06-08 14:51:31

If you want to use Gaussian to directly calculate gamma, see "examples\polar\NH3_gamma.gjf" in Multiwfn package for example. See Section 4.200.7 of Multiwfn manual for example.

If you want to use Multiwfn to calculate gamma based on SOS formalism, do not specify "polar" keyword, in current case you should only specify "TD(nstates=x)" and "IOp(9/40=5)". See Section 4.200.8 of Multiwfn manual for example.

anupthms000 · 2020-06-19 10:36:37

Dear sir
Some people are using 3 state model, two state model . Is it possible to get those results using Multiwfn . Look forward to hear from you.

Thank you

sobereva · 2020-06-19 11:20:13

Current latest version of Multiwfn is able to perform two-state model and three-state model analysis for beta, see Section 3.200.8.2 of manual for introduction and Section 4.200.8.2 for analysis example.

cvalverde · 2020-06-22 10:57:44

Using the SOS model, in the alpha output file (average linear polarizability) to convert the values to esu just multiply by 1.4819E-25 and in the case of gamma by 5.03670E-40.

Is this information correct?

sobereva · 2020-06-22 12:11:22

cvalverde wrote:

Using the SOS model, in the alpha output file (average linear polarizability) to convert the values to esu just multiply by 1.4819E-25 and in the case of gamma by 5.03670E-40.
Is this information correct?

This is correct if current values are in a.u.

choconostle123 · 2020-09-17 23:27:45

Hi, first i want to thank for the program in the last days this program and the manual has helped me a lot, and i want to ask about, which value can i use of my output of SOS to compare with the experimental value? in the paper are reported beta(zero) in 9 esu (they extrapolated the experimental value measure at 1580 nm), i have in my output of SOS of beta(0,0) the next data (adjoint picture), but i don't know which value i have to converted to esu and copare with the experimental value

Last edited by choconostle123 (2020-09-17 23:33:36)

sobereva · 2020-09-18 12:41:31

choconostle123 wrote:

Hi, first i want to thank for the program in the last days this program and the manual has helped me a lot, and i want to ask about, which value can i use of my output of SOS to compare with the experimental value? in the paper are reported beta(zero) in 9 esu (they extrapolated the experimental value measure at 1580 nm), i have in my output of SOS of beta(0,0) the next data (adjoint picture), but i don't know which value i have to converted to esu and copare with the experimental value
https://i.postimg.cc/G84VDzvK/image.png

The "Projection of beta on dipole moment" can be determined by EFISHG (electric field induced second harmonic generation) experiment, therefore if your have EFISHG experiment data at a frequency w, you should calculate SHG form of beta at w and then compare the "Projection of beta on dipole moment" with experiment.

Note that the static beta, namely beta(0;0,0), cannot be determined experimentally in principle.

choconostle123 · 2020-09-25 17:19:46

very grateful for the answer finally i can compare my values with the experimental values, and i want to comment a doubt in the meaning of the columns of the file beta_n because at difference with the file beta_n_comp in this file the meaning of each column appers but in the file beta_n don't appers i tried open with txt and opera (adjoint picture)

sobereva · 2020-09-26 02:10:58

choconostle123 wrote:

very grateful for the answer finally i can compare my values with the experimental values, and i want to comment a doubt in the meaning of the columns of the file beta_n because at difference with the file beta_n_comp in this file the meaning of each column appers but in the file beta_n don't appers i tried open with txt and opera (adjoint picture)
https://i.postimg.cc/kRdMP0jv/image.png
https://i.postimg.cc/vDMDjnpF/image.png

Please careful check prompts on screen when Multiwfn export the files, the meaning of each column is also shown explicitly.

valverde · 2020-11-12 17:51:49

I needed to calculate the SOS with non equilibrium salvation.
I used the following input:

%nosave
%nprocshared=40
%chk=g22_sos_bc.chk
%mem=40GB
#p cam-b3lyp/6-311++G(d,p) SCRF=(iefpcm,Solvent=dmso,NonEquilibrium=Save)

Solvente dmso

0 1
16 1.540108000 3.744434000 2.898043000
8 3.837623000 6.411342000 1.126905000
8 8.890953000 7.199642000 2.094155000

--link1--
%rwf=/Storage01/TempG09/clodoaldo/g22_sos_bc
%int=/Storage01/TempG09/clodoaldo/g22_sos_bc
%d2e=/Storage01/TempG09/clodoaldo/g22_sos_bc
%nosave
%nprocshared=40
%chk=g22_sos_bc.chk
%mem=40GB
#p cam-b3lyp/6-311++G(d,p) td=(nstates=300,root=1) IOp(9/40=5) Geom=Check Guess=Read SCRF=(iefpcm,Solvent=dmso,ExternalIteration,NonEquilibrium=Read)

Solvente dmso

0 1

but it works with 1500 states in multiwfn and not 300

sobereva · 2020-11-12 20:53:45

valverde wrote:

I needed to calculate the SOS with non equilibrium salvation.
I used the following input:
%nosave
...

I have fixed this problem and updated Multiwfn 3.8(dev) on Multiwfn website, please download the latest version and retry.

francesco ciccarello · 2023-12-20 16:58:12

Hi Tian,

firstly let me thank you for this super helpful program.
I am trying to calculate SFG and SDG hyperpolarizability with one frequency in IR, but Gaussian allows only to address the SHG hyperpolarizability.
Can I use the function number 19 of the Multiwfn hyperpolarizabilities menu "scanning w1 and w2 of beta" to get it,scanning the IR frequency?How much is accurate for small molecules?
Because I run it and it gave me back a really simple curve for the IR dependency, I think it takes into account only the electronic contribution to beta, neglecting the vibronic resonant ones, am I right? Could you suggest me a way to include theme?
Best regards,
Francesco

Last edited by francesco ciccarello (2023-12-20 16:59:24)

sobereva · 2023-12-20 18:24:08

Dear Francesco,

Yes, vibrational contribution is not considered in the SOS calculation in Multiwfn.

Best,

Tian

francesco ciccarello · 2023-12-21 18:02:24

Hi Tian,thank you for your quick answer.
Maybe I found a way to get also the vibronic contribution.
Do you know if I can get the dynamic polarizability only for the ground state?
Because I slightly modify the molecule along one normal mode but now Gaussian gives me back only the alpha static without also computing beta, even if I put CPHF and polar keyword.
Do you know why?

Last edited by francesco ciccarello (2023-12-21 18:41:16)

sobereva · 2023-12-21 20:24:56

I don't know why. This observation should be independent of choice of molecular structure.

Multiwfn forum

#1 2019-07-05 18:50:08

SOS computation of dipole hyperpolarizabilities

#2 2019-07-06 15:07:13

Re: SOS computation of dipole hyperpolarizabilities

#3 2019-07-08 09:37:09

Re: SOS computation of dipole hyperpolarizabilities

#4 2019-07-09 11:07:49

Re: SOS computation of dipole hyperpolarizabilities

#5 2019-07-23 06:15:48

Re: SOS computation of dipole hyperpolarizabilities

#6 2019-07-24 19:55:35

Re: SOS computation of dipole hyperpolarizabilities

#7 2019-08-06 17:51:18

Re: SOS computation of dipole hyperpolarizabilities

#8 2020-06-08 10:36:27

Re: SOS computation of dipole hyperpolarizabilities

#9 2020-06-08 11:10:28

Re: SOS computation of dipole hyperpolarizabilities

#10 2020-06-08 11:26:30

Re: SOS computation of dipole hyperpolarizabilities

#11 2020-06-08 14:51:31

Re: SOS computation of dipole hyperpolarizabilities

#12 2020-06-19 10:36:37

Re: SOS computation of dipole hyperpolarizabilities

#13 2020-06-19 11:20:13

Re: SOS computation of dipole hyperpolarizabilities

#14 2020-06-22 10:57:44

Re: SOS computation of dipole hyperpolarizabilities

#15 2020-06-22 12:11:22

Re: SOS computation of dipole hyperpolarizabilities

#16 2020-09-17 23:27:45

Re: SOS computation of dipole hyperpolarizabilities

#17 2020-09-18 12:41:31

Re: SOS computation of dipole hyperpolarizabilities

#18 2020-09-25 17:19:46

Re: SOS computation of dipole hyperpolarizabilities

#19 2020-09-26 02:10:58

Re: SOS computation of dipole hyperpolarizabilities

#20 2020-11-12 17:51:49

Re: SOS computation of dipole hyperpolarizabilities

#21 2020-11-12 20:53:45

Re: SOS computation of dipole hyperpolarizabilities

#22 2023-12-20 16:58:12

Re: SOS computation of dipole hyperpolarizabilities

#23 2023-12-20 18:24:08

Re: SOS computation of dipole hyperpolarizabilities

#24 2023-12-21 18:02:24

Re: SOS computation of dipole hyperpolarizabilities

#25 2023-12-21 20:24:56

Re: SOS computation of dipole hyperpolarizabilities

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