Problems with vibrational analysis with DFT and PCM

Find answers or ask questions regarding Dalton calculations.
Please upload an output file showing the problem, if applicable.
(It is not necessary to upload input files, they can be found in the output file.)

Post Reply
sauer
Posts: 45
Joined: 27 Aug 2013, 16:37
First name(s): Stephan P. A.
Last name(s): Sauer
Affiliation: Department of Chemistry, University of Copenhagen
Country: Denmark
Contact:

Problems with vibrational analysis with DFT and PCM

Post by sauer » 08 Oct 2019, 14:51

Hi everybody,

we are trying to do run a geometry optimization and vibrational analysis of a molecule in PCM at the DFT level, but have problems. Apparently one has to use numerical derivatives for the Hessian. But asking for this we get a
"MEMCHK ERROR, not a valid memget id in work(kalloc-1)". See the attached output file, which also includes in the input files.

But maybe we are using the wrong keywords to get this.

Any help would be appreciated.
Stephan
Attachments
opt-1_vand.out
(191.83 KiB) Downloaded 11 times

User avatar
magnus
Posts: 478
Joined: 27 Jun 2013, 16:32
First name(s): Jógvan Magnus
Middle name(s): Haugaard
Last name(s): Olsen
Affiliation: Hylleraas Centre, UiT The Arctic University of Norway
Country: Norway

Re: Problems with vibrational analysis with DFT and PCM

Post by magnus » 10 Oct 2019, 13:43

Looks like a bug which is possibly connected with switches between symmetries during numerical differentiation. Unfortunately, turning off symmetry doesn't work because of another bug.

In any case, I would run this in two steps. First do a geometry optimization and then perform vibrational analysis using the optimized geometry (and numerical Hessian).

sauer
Posts: 45
Joined: 27 Aug 2013, 16:37
First name(s): Stephan P. A.
Last name(s): Sauer
Affiliation: Department of Chemistry, University of Copenhagen
Country: Denmark
Contact:

Re: Problems with vibrational analysis with DFT and PCM

Post by sauer » 10 Oct 2019, 19:45

Hi Magnus,

thanks for looking at this. Unfortunately, running it in two steps does not help either. It runs in the same bugs. It is a bit strange, because it must mean, that nobody does DFT/PCM geometry optimizations with Dalton.

Stephan

User avatar
magnus
Posts: 478
Joined: 27 Jun 2013, 16:32
First name(s): Jógvan Magnus
Middle name(s): Haugaard
Last name(s): Olsen
Affiliation: Hylleraas Centre, UiT The Arctic University of Norway
Country: Norway

Re: Problems with vibrational analysis with DFT and PCM

Post by magnus » 10 Oct 2019, 19:57

Sorry I didn't mean to imply that it works if you run out in two steps. That was to avoid the calculation of a numerical Hessian in the geometry optimization step where it is not needed.

The geometry optimization works if you do not ask for the numerical Hessian. However, it is done with a fixed cavity according to Kenneth and I'm not exactly sure what the implication of that is.

The error you get is because of a bug in the calculation of the numerical Hessian when you include PCM.

User avatar
magnus
Posts: 478
Joined: 27 Jun 2013, 16:32
First name(s): Jógvan Magnus
Middle name(s): Haugaard
Last name(s): Olsen
Affiliation: Hylleraas Centre, UiT The Arctic University of Norway
Country: Norway

Re: Problems with vibrational analysis with DFT and PCM

Post by magnus » 10 Oct 2019, 20:00

If the bug is related to switching symmetry as I suspect then perhaps it can be avoided if symmetry detection is turned off. Unfortunately specifying "NoSymmetry" in the molecule file is not enough.

sauer
Posts: 45
Joined: 27 Aug 2013, 16:37
First name(s): Stephan P. A.
Last name(s): Sauer
Affiliation: Department of Chemistry, University of Copenhagen
Country: Denmark
Contact:

Re: Problems with vibrational analysis with DFT and PCM

Post by sauer » 10 Oct 2019, 20:29

And you do not happen to know where I could turn it off hard-code in the program?

xiongyan21
Posts: 183
Joined: 24 Sep 2014, 08:36
First name(s): yan
Last name(s): xiong
Affiliation: CENTRAL CHINA NORMAL UNIVERSITY
Country: China

Re: Problems with vibrational analysis with DFT and PCM

Post by xiongyan21 » 10 Oct 2019, 23:21

GAMESS can easily incorporate PCM into DFT and TDDFT calculations, and I just have successfully tried a UHF spin-flip TDDFT geometry optimization of a pesticide molecule for its triplet state in water, obtaining 5 states preset.
I will look into the s-squared.
Perhaps I also can use the geometry obtained for adiabatically using pcm for its phosphorescence calculation, vertical or adiabatic, in water with Dalton.
Last edited by xiongyan21 on 12 Oct 2019, 12:17, edited 5 times in total.

User avatar
magnus
Posts: 478
Joined: 27 Jun 2013, 16:32
First name(s): Jógvan Magnus
Middle name(s): Haugaard
Last name(s): Olsen
Affiliation: Hylleraas Centre, UiT The Arctic University of Norway
Country: Norway

Re: Problems with vibrational analysis with DFT and PCM

Post by magnus » 11 Oct 2019, 08:21

sauer wrote:
10 Oct 2019, 20:29
And you do not happen to know where I could turn it off hard-code in the program?
Not very specific but somewhere in DALTON/abacus/abander.F.

sauer
Posts: 45
Joined: 27 Aug 2013, 16:37
First name(s): Stephan P. A.
Last name(s): Sauer
Affiliation: Department of Chemistry, University of Copenhagen
Country: Denmark
Contact:

Re: Problems with vibrational analysis with DFT and PCM

Post by sauer » 11 Oct 2019, 09:30

Ok, thanks.

Post Reply

Who is online

Users browsing this forum: No registered users and 3 guests