CCL:G: Low-progression Franck-Condon transitions
- From: tianxiaohui,,zju.edu.cn
- Subject: CCL:G: Low-progression Franck-Condon transitions
- Date: Sun, 4 Nov 2018 22:04:53 +0800 (GMT+08:00)
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" <owner-chemistry]^[ccl.net>
> 发送时间: 2018-11-02 05:08:07
(星期五)
> 收件人: "Tian, Xiaohui "
<tianxiaohui]^[zju.edu.cn>
> 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"
<owner-chemistry],[ccl.net>
> To: "Bloino, Julien " <julien.bloino],[gmail.com>
> 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
> >><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
> >
> >
> >-= This is automatically added to each message by the mailing script
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> ><p style="margin-top:0;margin-bottom:0">Dear
Jan,</p>
> ><p style="margin-top:0;margin-bottom:0"><br>
> ></p>
> ><p style="margin-top:0;margin-bottom:0">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.</p>
> ><p style="margin-top:0;margin-bottom:0"><br>
> ></p>
> ><p
style="margin-top:0;margin-bottom:0">Nonetheless, I might
try
> >one of your suggestions as well, thanks for pointing me in this
> >direction.</p>
> ><p style="margin-top:0;margin-bottom:0"><br>
> ></p>
> ><p style="margin-top:0;margin-bottom:0">Best,</p>
> ><p style="margin-top:0;margin-bottom:0"><br>
> ></p>
> ><p
style="margin-top:0;margin-bottom:0">Tobias</p>
> ><p style="margin-top:0;margin-bottom:0">
</p>
> ><p style="margin-top:0;margin-bottom:0"><br>
> ></p>
> ><div id="Signature">
> ><div id="divtagdefaultwrapper" dir="ltr"
style="font-size: 12pt; color:
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> ><p class="x_MsoNormal" style="margin:0cm 0cm
0.0001pt; font-size:12pt;
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color:rgb(33,33,33)">
> ><span style="font-size:9pt;
> >font-family:Arial,sans-serif,serif,EmojiFont;
> >color:rgb(35,31,32)"><b>Dr Tobias
Krämer</b></span></p>
> ><p class="x_MsoNormal" style="margin:0cm 0cm
0.0001pt; font-size:12pt;
> >font-family:"Times New Roman",serif;
color:rgb(33,33,33)">
> ><span style="color:rgb(35,31,32);
> >font-family:Arial,sans-serif,serif,EmojiFont;
font-size:9pt">Lecturer
> >in Inorganic Chemistry</span><br>
> ></p>
> ><p class="x_MsoNormal" style="margin:0cm 0cm
0.0001pt; font-size:12pt;
> >font-family:"Times New Roman",serif;
color:rgb(33,33,33)">
> ><span style="color:rgb(35,31,32);
> >font-family:Arial,sans-serif,serif,EmojiFont;
font-size:9pt">Department
> >of Chemistry</span></p>
> ><p class="x_MsoNormal" style="margin:0cm 0cm
0.0001pt; font-size:12pt;
> >font-family:"Times New Roman",serif;
color:rgb(33,33,33)">
> ><span style="font-size:9pt;
> >font-family:Arial,sans-serif,serif,EmojiFont;
> >color:rgb(35,31,32)">Maynooth
University </span></p>
> ><p class="x_MsoNormal" style="margin:0cm 0cm
0.0001pt; font-size:12pt;
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color:rgb(33,33,33)">
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> >style="font-family:Arial-BoldMT,serif,EmojiFont;
> >color:rgb(35,31,32)"><img class="EmojiInsert"
width="145" height="89"
> >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"></span></b><br>
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> ><span style="font-size:9pt;
> >font-family:Arial,sans-serif,serif,EmojiFont;
> >color:rgb(35,31,32)">Maynooth University, Maynooth, Co.
Kildare,
> >Ireland.</span></p>
> ><p class="x_MsoNormal" style="margin:0cm 0cm
0.0001pt; font-size:12pt;
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>color:rgb(35,31,32)">E: </span></b><span
style="font-size:9pt;
> >font-family:Arial,sans-serif,serif,EmojiFont;
>
>color:rgb(35,31,32)">tobias.kraemer|-|mu.ie <b>T</b><b>:</b> +353
> >(0)1 474 7517</span></p>
> ><p
style="font-family:Calibri,Arial,Helvetica,sans-serif,"Apple
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> ><i><span style="font-size:10pt;
>
>font-family:Cambria,serif,serif,EmojiFont"></span></i></p>
> ></div>
> ></div>
> ></div>
> ><hr style="display:inline-block;width:98%"
tabindex="-1">
> ><div id="divRplyFwdMsg" dir="ltr"><font
face="Calibri, sans-serif"
> >style="font-size:11pt"
color="#000000"><b>From:</b>
> >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><br>
> ><b>Sent:</b> Saturday, October 27, 2018 4:25:23
PM<br>
> ><b>To:</b> Tobias Kraemer<br>
> ><b>Subject:</b> CCL:G: Low-progression Franck-Condon
transitions</font>
> ><div> </div>
> ></div>
> ><div class="BodyFragment"><font
size="2"><span style="font-size:11pt;">
> ><div class="PlainText"><br>
> >Sent to CCL by: =?UTF-8?Q?Jan_G=c3=b6tze?=
> >[jgoetze##zedat.fu-berlin.de]<br>
> >Dear Tobias,<br>
> ><br>
> >the data you provided only allow for limited analysis why your proble
> ><br>
> >occurs. In case you did not do any errors in preparation of your two
> ><br>
> >excited states, it appears that the minima of ground and excited state
> ><br>
> >are very distant from each other (such as groups rotating, and/or
> >normal <br>
> >modes differing strongly between ground and excited state). For a
> >large, <br>
> >planar, aromatic system like pc this is rather unusual. As such,
> >without <br>
> >further details on the molecular structure, any additional help can
> >only <br>
> >be guesswork.<br>
> ><br>
> >To obtain a preliminary spectrum quickly and often without problems, I
> ><br>
> >personally would suggest using a vertical TD approach, which might be
> ><br>
> >available in Gaussian16, or an IMDHO-FA as in ORCA. See for example
> ><br>
> >doi:10.1021/ct500830a<br>
> ><br>
> >Cheers,<br>
> >Jan<br>
> ><br>
> >Am 26.10.2018 um 12:57 schrieb Tobias Kraemer
> >tobias.kraemer[a]mu.ie:<br>
> >> Sent to CCL by: "Tobias Kraemer"
> >[tobias.kraemer_._mu.ie]<br>
> >> Hello everyone,<br>
> >><br>
> >> I am interested in calculating vibrationally-resolved spectra
in
> >G16. The<br>
> >> molecule in question is a phthalocyanine (pc) complex. I've
> >followed the<br>
> >> protocol detailed in the whitepaper by Barone et al., however
in
> >the<br>
> >> final step (generating the spectrum) an error
occurs:<br>
> >><br>
> >><br>
> >>
> >==================================================<br>
>
>>
> >Calculations of Band Intensities<br>
> >>
> >==================================================<br>
> >><br>
> >> -- To: vibronic fundamental state
--<br>
> >> Spectrum
> >progression: 0.06%<br>
> >><br>
> >> -- To: single overtones --<br>
> >> Spectrum
> >progression: 0.71%<br>
> >><br>
> >> -- To: combinations of 2
simultaneously excited
> >modes --<br>
> >> Spectrum
> >progression: 4.14%<br>
> >><br>
> >> ERROR: Low progression after class 2.
Total
> >convergence = 4.1%.<br>
>
>>
The vibronic
> >spectrum will likely be unreliable. Stopping.<br>
> >><br>
> >> 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<br>
> >> optimisation I have included 6 states, of which the gradients
for
> >the<br>
> >> first one are to be followed
[TD=(Read,NStates=6,Root=1)].<br>
> >> There are a good number of keywords listed on the Gaussian16
> >webpage that<br>
> >> relate to this type of calculation, and I'd appreciate some
> >guidance on<br>
> >> the above issue and possible ways around it.<br>
> >><br>
> >> Thanks for your help, as always much appreciated.<br>
> >><br>
> >> Kind regards,<br>
> >><br>
> >> Tobias<br>
> ><br>
> ><br>
> >-= This is automatically added to each message by the mailing script
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