From owner-chemistry@ccl.net Tue Oct 30 01:39:00 2018 From: "Tobias Kraemer Tobias.Kraemer!A!mu.ie" To: CCL Subject: CCL:G: Low-progression Franck-Condon transitions Message-Id: <-53533-181029223705-12063-E89d1liw94YrZPwA/AECLQ###server.ccl.net> X-Original-From: Tobias Kraemer Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_DB7PR02MB40905EFC8A6B3A0AA05CCEBE8BCC0DB7PR02MB4090eurp_" Date: Tue, 30 Oct 2018 02:36:55 +0000 MIME-Version: 1.0 Sent to CCL by: Tobias Kraemer [Tobias.Kraemer**mu.ie] --_000_DB7PR02MB40905EFC8A6B3A0AA05CCEBE8BCC0DB7PR02MB4090eurp_ Content-Type: text/plain; charset="iso-8859-1" Content-Transfer-Encoding: quoted-printable Dear Jan, thanks for your reply. Sorry for being so unspecific in my post, I thought = this was a more generic error that could be solved more easily. You are rig= ht about the fact that the geometries of the ground and excited state of th= is ZnPc complex differ (not too a large extend, but obviously enough). The = ground state is planar with D4h symmetry, while the structure of the (1st) = excited state converges to a C2v-symmetric geometry (consistent with litera= ture J. Chem. Phys., 2015, 142, 094310). In fact the white paper by Barone = "Vibrationally-excited states in Gaussian09" mentions the distortion of the= excited state geometry away from a planar geometry in the ground state can= cause problems (and FC does not apply). However, since the aforementioned = paper in J. Chem. Phys. presents a FC spectrum, I believe that it must stil= l be possible to generate the spectrum, and find a way around this issue. I= should also mention that by visual inspection the excited state geometry i= s not hugely different from the ground state (but obviously large enough to= cause a problem). It seems in G09 one could force the plot of a spectrum n= onetheless, via FORCEPRTSPECTRUM. My question was also regarding a range of= other keywords that might be useful here (MAXBANDS/MAXC1/MAXOVR..). So the= question still stands, since I think it must be possible to solve this iss= ue. Nonetheless, I might try one of your suggestions as well, thanks for pointi= ng me in this direction. Best, Tobias Dr Tobias Kr=E4mer Lecturer in Inorganic Chemistry Department of Chemistry Maynooth University [Maynooth University PNG Trans] Maynooth University, Maynooth, Co. Kildare, Ireland. E: tobias.kraemer() mu.ie T: +353 (0)1 474 7517 ________________________________ > From: owner-chemistry+tobias.kraemer=3D=3Dmu.ie() ccl.net on behalf of Jan G=F6tze jgoetze[]zedat.fu= -berlin.de Sent: Saturday, October 27, 2018 4:25:23 PM To: Tobias Kraemer Subject: CCL:G: Low-progression Franck-Condon transitions Sent to CCL by: =3D?UTF-8?Q?Jan_G=3Dc3=3Db6tze?=3D [jgoetze##zedat.fu-berli= n.de] Dear Tobias, the data you provided only allow for limited analysis why your proble occurs. In case you did not do any errors in preparation of your two excited states, it appears that the minima of ground and excited state are very distant from each other (such as groups rotating, and/or normal modes differing strongly between ground and excited state). For a large, planar, aromatic system like pc this is rather unusual. As such, without further details on the molecular structure, any additional help can only be guesswork. To obtain a preliminary spectrum quickly and often without problems, I personally would suggest using a vertical TD approach, which might be available in Gaussian16, or an IMDHO-FA as in ORCA. See for example doi:10.1021/ct500830a Cheers, Jan Am 26.10.2018 um 12:57 schrieb Tobias Kraemer tobias.kraemer[a]mu.ie: > Sent to CCL by: "Tobias Kraemer" [tobias.kraemer_._mu.ie] > Hello everyone, > > I am interested in calculating vibrationally-resolved spectra in G16. The > molecule in question is a phthalocyanine (pc) complex. I've followed the > protocol detailed in the whitepaper by Barone et al., however in the > final step (generating the spectrum) an error occurs: > > > =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D > Calculations of Band Intensities > =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D > > -- To: vibronic fundamental state -- > Spectrum progression: 0.06% > > -- To: single overtones -- > Spectrum progression: 0.71% > > -- To: combinations of 2 simultaneously excited modes -- > Spectrum progression: 4.14% > > ERROR: Low progression after class 2. Total convergence =3D 4.1%. > The vibronic spectrum will likely be unreliable. Stopping. > > The whitepaper provides some possible causes, but I'd like to ask for > some expert opinions here on CCL nonetheless. In the excited state > optimisation I have included 6 states, of which the gradients for the > first one are to be followed [TD=3D(Read,NStates=3D6,Root=3D1)]. > There are a good number of keywords listed on the Gaussian16 webpage that > relate to this type of calculation, and I'd appreciate some guidance on > the above issue and possible ways around it. > > Thanks for your help, as always much appreciated. > > Kind regards, > > Tobias -=3D This is automatically added to each message by the mailing script =3D-http://www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt--_000_DB7PR02MB40905EFC8A6B3A0AA05CCEBE8BCC0DB7PR02MB4090eurp_ Content-Type: text/html; charset="iso-8859-1" Content-Transfer-Encoding: quoted-printable

Dear Jan,


thanks for your reply. Sorry for = being so unspecific in my post, I thought this was a more generic error tha= t could be solved more easily. You are right about the fact that the geomet= ries of the ground and excited state of this ZnPc complex differ (not too a large extend, but obviously en= ough). The ground state is planar with D4h symmetry, while the structure of= the (1st) excited state converges to a C2v-symmetric geometry (c= onsistent with literature J. Chem. Phys., 2015, 142, 094310). In fact the white paper by Barone "Vibrationally-excite= d states in Gaussian09" mentions the distortion of the excited state g= eometry away from a planar geometry in the ground state can cause problems = (and FC does not apply). However, since the aforementioned paper in J. Chem. Phys. presents a FC spectrum, I believe t= hat it must still be possible to generate the spectrum, and find a way arou= nd this issue. I should also mention that by visual inspection the exc= ited state geometry is not hugely different from the ground state (but obviously large enough to cause a problem). It = seems in G09 one could force the plot of a spectrum nonetheless, via FORCEP= RTSPECTRUM. My question was also regarding a range of other keywords that m= ight be useful here (MAXBANDS/MAXC1/MAXOVR..). So the question still stands, since I think it must be possible to solve t= his issue.


Nonetheless, I might try one= of your suggestions as well, thanks for pointing me in this direction.


Best,


Tobias

   


Dr Tobias Kr=E4mer

Lecturer in Inorganic Chemistry

Department of Chemistry

Maynooth University 

3D"Maynooth

Maynooth University, Maynooth, Co. Kildare, Ireland.<= /span>

E: tobias.kraemer() mu.ie T: +353 (0)1 474 7517

From: owner-chemistry+t= obias.kraemer=3D=3Dmu.ie() ccl.net <owner-chemistry+tobias.kraemer=3D= =3Dmu.ie() ccl.net> on behalf of Jan G=F6tze jgoetze[]zedat.fu-berlin.de <owner-chemistry() ccl.net>
Sent: Saturday, October 27, 2018 4:25:23 PM
To: Tobias Kraemer
Subject: CCL:G: Low-progression Franck-Condon transitions
 

Sent to CCL by: =3D?UTF-8?Q?Jan_G=3Dc3=3Db6tze?=3D [jgoetze##zedat.fu-berli= n.de]
Dear Tobias,

the data you provided only allow for limited analysis why your proble
occurs. In case you did not do any errors in preparation of your two
excited states, it appears that the minima of ground and excited state
are very distant from each other (such as groups rotating, and/or normal modes differing strongly between ground and excited state). For a large, planar, aromatic system like pc this is rather unusual. As such, without further details on the molecular structure, any additional help can only be guesswork.

To obtain a preliminary spectrum quickly and often without problems, I
personally would suggest using a vertical TD approach, which might be
available in Gaussian16, or an IMDHO-FA as in ORCA. See for example
doi:10.1021/ct500830a

Cheers,
Jan

Am 26.10.2018 um 12:57 schrieb Tobias Kraemer tobias.kraemer[a]mu.ie:
> Sent to CCL by: "Tobias  Kraemer" [tobias.kraemer_._mu.= ie]
> Hello everyone,
>
> I am interested in calculating vibrationally-resolved spectra in G16. = The
> molecule in question is a phthalocyanine (pc) complex. I've followed t= he
> protocol detailed in the whitepaper by Barone et al., however in the > final step (generating the spectrum) an error occurs:
>
>
>       =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D
>            = ;    Calculations of Band Intensities
>       =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D= =3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D
>
>   -- To: vibronic fundamental state --
>      Spectrum progression:    = 0.06%
>
>   -- To: single overtones --
>      Spectrum progression:    = 0.71%
>
>   -- To: combinations of  2 simultaneously excited mode= s --
>      Spectrum progression:    = 4.14%
>
>   ERROR: Low progression after class 2. Total convergence = =3D  4.1%.
>          The vibronic spe= ctrum will likely be unreliable. Stopping.
>
> The whitepaper provides some possible causes, but I'd like to ask for<= br> > some expert opinions here on CCL nonetheless. In the excited state
> optimisation I have included 6 states, of which the gradients for the<= br> > first one are to be followed [TD=3D(Read,NStates=3D6,Root=3D1)].
> There are a good number of keywords listed on the Gaussian16 webpage t= hat
> relate to this type of calculation, and I'd appreciate some guidance o= n
> the above issue and possible ways around it.
>
> Thanks for your help, as always much appreciated.
>
> Kind regards,
>
> Tobias


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