Multiwfn forum

tdog123

Member

Registered: 2023-03-08

Posts: 7

Multiwfn output differs from ORCA output

Hello everybody,

I calculated transition and permanent, magnetic and electric dipole moments with ORCA and afterwards with Multiwfn.
My problem is that the results differ from the ORCA output file, i.e. the electric transition dipole moments (0 -> 1, 0 -> 2, ...).
Can someone tell me what Multiwfn is exactly doing and why those results are different?
The other results are not in the expected range (comparison with the experiment) as well.

Thanks in advance.

best regards,
Thomas

tdog123

Member

Registered: 2023-03-08

Posts: 7

Re: Multiwfn output differs from ORCA output

I meant that I calculated with ORCA the electric transition dipole moments and afterwards all dipole moments with Multiwfn,

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,777

Website

Re: Multiwfn output differs from ORCA output

Two possible reasons:
(1) You didn't specify "tprint 1E-8" in %tddft
(2) You performed TDDFT rather than TDA-DFT, in the former case the result should be inaccurate if de-excitation configurations contribute notably

For details, please check "ORCA users" in Part 3 of Section "3.21.A Basic information about electron excitation analysis module" in Multiwfn manual.

tdog123

Member

Registered: 2023-03-08

Posts: 7

Re: Multiwfn output differs from ORCA output

Hi Tian Lu,

thank you for your quick response.
I tried your advices but the results are still not as aspected.

This is the input-file I used:

! wB97X-D3BJ def2-SVP def2/J RIJCOSX TightSCF

%pal nprocs 32
end

%TDDFT
NROOTS 3
TDA true
TPRINT 1E-8
END

%output
PrintLevel Normal
#Print[ P_MOs ] 1
#Print[ P_Overlap ] 1
end

#%cpcm
#epsilon 4.0
#end

* xyzfile 0 1 cla2_opt.xyz

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,777

Website

Re: Multiwfn output differs from ORCA output

There is not evident problem from your input file.

To reproduce your observation, I need your .molden.input file and ORCA output file, you may compress and share them via file hosting service and paste downloading link here, I will check. Alternatively, send them to my E-mail.

tdog123

Member

Registered: 2023-03-08

Posts: 7

Re: Multiwfn output differs from ORCA output

Ok.

I send you a dropbox link. Is this ok?

https://www.dropbox.com/s/6gxb1ad56w85q … input?dl=0

https://www.dropbox.com/s/vs9pqxmem11wl … 2.out?dl=0

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,777

Website

Re: Multiwfn output differs from ORCA output

I have checked your file, the result printed by subfunction 5 of main function 18 Multiwfn is in good agreement with ORCA

Those printed by Multiwfn:

Transition electric dipole moment between ground state (0) and excited states ( a.u.) i j X Y Z Diff.(eV) Oscil.str 0 1 1.2200139 1.7805647 0.3778114 2.26800 0.26680 0 2 -0.6526576 -0.1042663 -0.0162139 2.76200 0.02958 0 3 -0.9657421 0.9433320 0.3632050 3.84700 0.18421

Those outputted by ORCA

----------------------------------------------------------------------------- ABSORPTION SPECTRUM VIA TRANSITION ELECTRIC DIPOLE MOMENTS ----------------------------------------------------------------------------- State Energy Wavelength fosc T2 TX TY TZ (cm-1) (nm) (au**2) (au) (au) (au) ----------------------------------------------------------------------------- 1 18292.8 546.7 0.265860026 4.78462 -1.21955 -1.77634 -0.37675 2 22279.3 448.8 0.029599100 0.43737 0.65295 0.10384 0.01572 3 31027.8 322.3 0.183715970 1.94927 0.96454 -0.94235 -0.36181

For example, the Y component of transition of S0-S1 given by Multiwfn is 1.7805647, the counterpart given by ORCA is -1.77634, the difference is quite small. The sign is different, because Multiwfn and ORCA employ different convention of electric dipole operator, this doesn't matter. If you hope to make the agreement even better, you can use TPRINT 1E-10, but the output file of ORCA will be larger.

tdog123

Member

Registered: 2023-03-08

Posts: 7

Re: Multiwfn output differs from ORCA output

I got the same result.
Thank you.

And what do you get for the permanent dipole moments (0 -> 0, 1 -> 1, 2 -> 2) and for the transition dipole moment from S1 to S2?
The permanent dipole moments are rather big.

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,777

Website

Re: Multiwfn output differs from ORCA output

Result:

Note: In below output the case of i=j corresponds to contribution of electron t o dipole moment of excited state i Transition electric dipole moment between excited states (a.u.): i j X Y Z Diff.(eV) Oscil.str 1 1 8.1128566 27.5325457 -11.1031678 0.00000 0.00000 1 2 -0.3564785 -0.9319312 -0.2005617 0.49400 0.01254 1 3 0.1879258 0.6038274 0.1079457 1.57900 0.01592 2 2 9.0731804 27.3089606 -11.2001798 0.00000 0.00000 2 3 0.0290171 -0.4554603 -0.0817156 1.08500 0.00571 3 3 6.8035680 24.7108321 -11.8004531 0.00000 0.00000

As mentioned in the prompt, the data like 1->1 only corresponds toelectroncontribution to the transition dipole moment. Therefore, if the center of nuclear charges is not at origin, you need to manually add contribution of nuclear charges to it to obtain electric dipole moment of excited state.

tdog123

Member

Registered: 2023-03-08

Posts: 7

Re: Multiwfn output differs from ORCA output

Thank you for that.

I took the coordinates of the atoms of the molden.input file but the value for the core dipole moment is way to large.
Do you know what the unit of the coordinates in the molden.input file is?

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,777

Website

Re: Multiwfn output differs from ORCA output

The unit is Bohr

tdog123

Member

Registered: 2023-03-08

Posts: 7

Re: Multiwfn output differs from ORCA output

Thank you.
Now everything is in the correct magnitude.