From owner-chemistry[ AT ]ccl.net Sun Nov 4 11:52:00 2018 From: "tianxiaohui|-|zju.edu.cn" To: CCL Subject: CCL:G: Low-progression Franck-Condon transitions Message-Id: <-53537-181104090611-4899-hScSqkiBlLHfV91k1KEFzQ[]server.ccl.net> X-Original-From: tianxiaohui,,zju.edu.cn Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset=UTF-8 Date: Sun, 4 Nov 2018 22:04:53 +0800 (GMT+08:00) MIME-Version: 1.0 Sent to CCL by: tianxiaohui..zju.edu.cn dear Dr Julien， Thank you. Your explanations are very helpful.  I am confused by the TI results showed in GaussView. I can find two spectra there，one is directly broadened from the sticks (legend: Spectrum from reported transitions). But the second one (legend: The final spectrum), also the one printed in Gaussian output file, usually has higher 0-1 0-2 peaks than the other. I 'd like to know the difference and which should I use？ By the way, the convergence of my TI result is 86.7%, is this value acceptable? Thanks a lot. Best regards. > from Tian. > -----原始邮件----- > 发件人: "Julien Bloino julien.bloino~!~gmail.com" > 发送时间: 2018-11-02 05:08:07 (星期五) > 收件人: "Tian, Xiaohui " > 抄送: > 主题: CCL:G: Low-progression Franck-Condon transitions > > > Sent to CCL by: "Julien Bloino" [julien.bloino:_:gmail.com] > Dear Dr. Krämer, > > As commented by Dr. Götze, the likely reason for the small progression > is a significant shift of one or more modes. > The keywords are for G16 and should be inserted in the `ReadFCHT` > section (Freq=ReadFCHT). > You can see the shift vector with > `Print=Matrix=K` > Depending on the symmetry and the structural changes, you may improve > the convergence by increasing the maximum number of quanta for the > overtones (MaxC1) and 2-modes combinations (MaxC2): > `Prescreening=(MaxC1=20,MaxC2=13)` (those are the default values.) > This is rarely sufficient to fix the convergence issue and you may want > to check the presence of low-frequency large amplitude modes (large > shift of low-energy modes) and potentially exclude them as they are > poorly treated with this model. > You can do them with: > `RedDim=Block` > followed by the list of modes to exclude (the reference state is the > lower state, so you will have to list the modes to exclude from the > initial state, compatible with the definition of the shift vector K). > Note that Gaussian will try to build a consistent set of modes (same > number in each state) to exclude from the vibronic treatment. It has a > safety check to stop if too many modes are selected this way compared to > the initial list. You can force it by changing the value of > `RedDim=BlockTol` > The definition of the set of modes to exclude is based on the Duschinsky > matrix, which can be printed with, > `Print=Matrix=J` (we generally always print both J and K with > `Print=Matrix=JK`) > Be careful in the truncation as the model system obtained this way may > not be representative of the full system anymore. > > To obtain a fully converged spectrum, you can use the time-dependent > formalism instead of the sum-over-states one (the default in this case) > with the option > `TimeDependent` > I would recommend to use first TI to setup your protocol (trying the > options described above) and once a sufficient convergence is reached, > use TD to obtain the full band-shape. Indeed, the breakdown of the > Franck-Condon approximation has a direct impact on a TI calculations > (low and slow convergence) but is difficult to detect within the TD > framework (the spectrum is always fully converged by definition). > > Regarding ForcePrtSpectrum, the option (and all "advanced" options) is > still there but I chose not to document it as it is a double-edged sword > and could be misinterpreted. There are technically 2 separate checks but > the one you mention will not be helpful in your case (at least in a > first time). > - the first test is on the overall convergence after 2-modes > combinations. If it is below 20% (which is the case here), Gaussian will > stop. You can override this with > `Advanced=ForceFCCalc` > - the second test is at the end of the calculations, before printing the > spectrum. If the progression is below 50%, the spectrum is not printed. > You can override this with > `Advanced=ForcePrtSpectrum` > > Regarding the description of the potential energy surfaces, Gaussian > supports AdiabaticHessian (AH, the default), AdiabaticShift (AS), > VerticalHessian (VH, also noted VFC) and VerticalGradient (VG, aka LCM > or IMDHO). From my understanding, a behavior similar to IMDHO-FA would > be obtained in Gaussian with > `VerticalHessian DataMod=Duschinsky=Identity` > Simplified models (like VG) should be used with care. While it is easier > to reach convergence with them, they can also misrepresent the actual > system, leading to incorrect spectra. The validity of such approximation > will depend on your system. > > I hope this will answer your questions regarding the progression and > keywords. > > Best regards, > > Julien Bloino > > ------ Original Message ------ > > From: "Tobias Kraemer Tobias.Kraemer!A!mu.ie" > To: "Bloino, Julien " > Sent: 2018-10-30 03:36:55 > Subject: CCL:G: Low-progression Franck-Condon transitions > > >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 right about the fact that the geometries of the ground and > >excited state of this 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 literature 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 > >still 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 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 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 issue. > > > > > >Nonetheless, I might try one of your suggestions as well, thanks for > >pointing me in this direction. > > > > > >Best, > > > > > >Tobias > > > > > > > > > >Dr Tobias Krämer > > > >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==mu.ie|-|ccl.net > >> on behalf of Jan > >>Götze 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: =?UTF-8?Q?Jan_G=c3=b6tze?= > >[jgoetze##zedat.fu-berlin.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: > >> > >> > >> ================================================== > >> Calculations of Band Intensities > >> ================================================== > >> > >> -- 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 = 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=(Read,NStates=6,Root=1)]. > >>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 > > > > > >-= This is automatically added to each message by the mailing script > >=-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 > > > > > > > > > > > > > > > >
>style="font-size:12pt;color:#000000;font-family:Calibri,Helvetica,sans-serif;" > >dir="ltr"> > >

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 right about the fact > >that the geometries of the ground and excited state > >of this 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 literature 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 still 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 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 > >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 issue.

> >


> >

> >

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

> >


> >

> >

Best,

> >


> >

> >

Tobias

> >

   

> >


> >

> >
> >
> >

> >Dr Tobias Krämer

> >

> >Lecturer > >in Inorganic Chemistry
> >

> >

> >Department > >of Chemistry

> >

> >Maynooth University 

> >

> > >style="font-family:Arial-BoldMT,serif,EmojiFont; > >color:rgb(35,31,32)"> >id="x_Picture_x0020_1" alt="Maynooth University PNG Trans" > >style="width:1.5104in; height:0.927in" data-outlook-trace="F:0|T:1" > >src="cid:image004.png|-|01D35E2B.48797380">
> >

> >

> >Maynooth University, Maynooth, Co. Kildare, > >Ireland.

> >

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

> >

> >

> >
> >
> >
> >
> >
>style="font-size:11pt" color="#000000">From: > >owner-chemistry+tobias.kraemer==mu.ie|-|ccl.net > ><owner-chemistry+tobias.kraemer==mu.ie|-|ccl.net> on behalf > >of Jan Götze 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: =?UTF-8?Q?Jan_G=c3=b6tze?= > >[jgoetze##zedat.fu-berlin.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:
> >>
> >>
> >>       > >==================================================
> >>                > >Calculations of Band Intensities
> >>       > >==================================================
> >>
> >>   -- 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 =  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=(Read,NStates=6,Root=1)].
> >> 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
> >
> >
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