From owner-chemistry@ccl.net Fri Dec 13 08:49:00 2013 From: "Harald Lanig harald.lanig() fau.de" To: CCL Subject: CCL: MGMS-DS: Molecular Modelling Workshop 2014 in Erlangen, Germany Message-Id: <-49442-131213042818-29680-2vGP9xSDdykErxznrQ88Lw.:.server.ccl.net> X-Original-From: Harald Lanig Content-Transfer-Encoding: 7bit Content-Type: text/plain; charset=ISO-8859-15; format=flowed Date: Fri, 13 Dec 2013 10:27:34 +0100 MIME-Version: 1.0 Sent to CCL by: Harald Lanig [harald.lanig*|*fau.de] Dear list subscribers, I am very happy to announce that also next year, the traditional Molecular Modelling Workshop in Erlangen (formerly known as "Darmstadt workshop") takes place on March, Monday 17th to Wednesday 19th, 2014. Starting on Monday after lunch should allow to avoid travelling on weekend keeping the expenses at a minimum. This time, the scientific program of the meeting is conducted by Klaus Liedl, University of Innsbruck, Austria. ####### Plenary Speakers ####### We are very happy to announce that two leading experts in their field have agreed to give a plenary talk at the meeting: John Chodera Memorial Sloan-Kettering Cancer Center, New York, USA Christofer Tautermann Boehringer-Ingelheim, Biberach, Germany ####### Poster and Lecture Awards ####### As in the past years, there will be two Poster Awards of EUR 100 each and three Lecture Awards for the best talks: 1st Winner: Travel bursary to the Young Modellers Forum in the United Kingdom (travel expenses are reimbursed up to EUR 500) 2nd Winner: EUR 200 travel expenses reimbursement 3rd Winner: EUR 100 travel expenses reimbursement Only undergraduate and graduate research students qualify for the poster and lecture awards. As every year, an interesting and successful workshop depends on your contributions. Therefore let me invite you to submit talks and/or poster titles via the registration form accessible on the workshop Web site http://mmws2014.mgms-ds.de/index.php?m=register This Web site will provide all necessary information about the meeting! The deadline for all submissions is February 14th, 2014. I am looking forward to meeting you in Erlangen soon! -Harald Lanig -- ------------------------------------------------------------------------ PD Dr. Harald Lanig Universitaet Erlangen/Nuernberg Zentralinstitut fuer Scientific Computing (ZISC) Geschaeftsfuehrer Martensstrasse 5a, 91058 Erlangen Fon +49 9131-85 27081 harald DOT lanig AT fau.de Fax +49 9131-85 27085 http://www.zisc.uni-erlangen.de Computer-Chemie-Centrum Naegelsbachstr. 25, 91052 Erlangen Fon +49 9131-85 26525 harald DOT lanig AT fau.de Fax +49 9131-85 26565 http://www.chemie.uni-erlangen.de/lanig ------------------------------------------------------------------------ From owner-chemistry@ccl.net Fri Dec 13 09:55:00 2013 From: "David A Case case|biomaps.rutgers.edu" To: CCL Subject: CCL:G: J constant in NMR Message-Id: <-49443-131213073919-16146-No4elLgUDRgLzjLKqbqcbg(-)server.ccl.net> X-Original-From: David A Case Content-Disposition: inline Content-Type: text/plain; charset=us-ascii Date: Fri, 13 Dec 2013 07:39:11 -0500 Mime-Version: 1.0 Sent to CCL by: David A Case [case .. biomaps.rutgers.edu] On Thu, Dec 12, 2013, Jim Kress ccl_nospam .. kressworks.com wrote: > > Use ORCA. It was designed for this. ORCA is fine, but so is Gaussian. > > Sent to CCL by: "mahnaz gh" [mahnaz271163 _ yahoo.com] Hi there I wanna see > the spin-spin coupling in the NMR of CH3-CH2Cl. The route section which I > selected is as follow:"# nmr=(giao,spinspin,mixed) b3lyp/6-311++g(d,p) > geom=connectivity". How can I see the spin-spin coupling and splitting in > the output file? Have you examined the output file? Is there not a section labeled: Total nuclear spin-spin coupling J (Hz) And other sections that give spin-spin coupling contributions? For me, the Gaussian output seems clear and self-explanatory. I usually use the "readatoms" option to the NMR keyword to select the particular couplings I want. ....dave case From owner-chemistry@ccl.net Fri Dec 13 10:29:00 2013 From: "M Gh mahnaz271163%%yahoo.com" To: CCL Subject: CCL:G: Modeling Antiferromagnetic Coupling in Gaussian 09 Message-Id: <-49444-131213100637-758-0mjyulirf3Zh8W4yEwMbzA .. server.ccl.net> X-Original-From: "M Gh" Date: Fri, 13 Dec 2013 10:06:36 -0500 Sent to CCL by: "M Gh" [mahnaz271163%x%yahoo.com] I'm new to Gaussian,so I try to reproduce some example at Gaussian's website:"Gaussian.com,Tech support, white papers, Modeling Antiferromagnetic Coupling in Gaussian 09".But I'm confused about one.After running the 2nd job, the output is different from mine. The output that mentioned in the Gaussian.com site is as follow: Stability analysis using singles matrix: *********************************************************************** Eigenvectors of the stability matrix: Eigenvector 1: ?Spin -B2G Eigenvalue=-0.0129755 75A -> 79A 0.68583 76A -> 80A 0.70288 Eigenvector 2: ?Spin -B1U Eigenvalue=-0.0066257 70A -> 79A -0.10926 75A -> 80A 0.37604 76A -> 79A 0.89115 Eigenvector 3: ?Spin -B3U Eigenvalue= 0.0058150 77A -> 80A -0.34398 78A -> 79A 0.92278 The wavefunction has an internal instability. my output is as follows: *********************************************************************** Stability analysis using singles matrix: *********************************************************************** Eigenvectors of the stability matrix: Eigenvector 1: 1.000-B1G Eigenvalue= 0.0272861 =0.000 78A -> 79A 0.99727 could anyone please help me with this question that where the difference comes from? Regards From owner-chemistry@ccl.net Fri Dec 13 11:05:00 2013 From: "Pierre Archirel pierre.archirel]*[u-psud.fr" To: CCL Subject: CCL:G: FC analysis after a TDDFT calculation Message-Id: <-49445-131213110341-5350-iMsFkmoTzocQYFvDluq9eA() server.ccl.net> X-Original-From: "Pierre Archirel" Date: Fri, 13 Dec 2013 11:03:40 -0500 Sent to CCL by: "Pierre Archirel" [pierre.archirel^_^u-psud.fr] Dear colleagues, I could optimise the geometry of an excited state with TDDFT and gaussian09. Asking for the Franck-Condon analysis (with simply freq=fc), I get the answer: ERROR: The Franck-Condon factor corresponding to the overlap integral between both vibrational ground states is too small: |<0'|0">|^2 < 0.47904E-13 I understand that the two geometries are very different, but how can I ask for upper vibrational levels in the excited state, so as to reach the FC zone? Many thanks in advance, Pierre Archirel LCP, universite Paris-Sud France pierre.archirel:u-psud.fr From owner-chemistry@ccl.net Fri Dec 13 12:56:00 2013 From: "Hao-Bo Guo guohaobo_._gmail.com" To: CCL Subject: CCL:G: SV: TDDFT (CAM-B3LYP) oscillator strength too high Message-Id: <-49446-131213111549-16101-IsJaOMXxN1GVcr0xxUhiwA..server.ccl.net> X-Original-From: Hao-Bo Guo Content-Type: multipart/alternative; boundary=e89a8ff1c94c02d91f04ed6cc568 Date: Fri, 13 Dec 2013 11:15:24 -0500 MIME-Version: 1.0 Sent to CCL by: Hao-Bo Guo [guohaobo_-_gmail.com] --e89a8ff1c94c02d91f04ed6cc568 Content-Type: text/plain; charset=ISO-8859-1 Dear Jen, Yeah, I've got it. I almost forgot without your reply! Because this is also how I generated the experimental band spectra from the line spectra calculated by TDDFT, eg., using Gaussian expansions: eps(nu) = (1/4.32E-9) * sigma[f_i * G(nu_i)] Thank you very much! Best regards, Hao-Bo On Thu, Dec 12, 2013 at 6:20 AM, Jens Spanget-Larsen spanget%%ruc.dk < owner-chemistry*|*ccl.net> wrote: > > > Dear Micaela and others! > > The f-sum rule may be stated as follows: > > > > The sum of all oscillator strengths, f(0,n), from a state |0> to all other > states |n> obeys the sum rule SUMMA(n) f(0,n) = N > > > > -- > > > f(0,n) = N > > -- > > n#0 > > > > where N is the total number of electrons in the system (also called the > Thomas-Reiche-Kuhn sum rule). > > > > This formulation is taken from Poul Joergensen & Jens Oddershede: > "Problems in quantum chemistry", Addison-Wesley, Massachusetts, USA, 1983. > Hence, the f-value for an electronic transition is not limited to > magnitudes below or equal to unity, it may increase unity. As a matter of > fact, it frequently does. For example, the experimental oscillator strength > for the first transition in all-trans beta-carotene is equal to f = 2.7. > This is the value obtained by integration over the absorption band in > hexane with maximum at 22200 cm-1 and eps = 139400 ( > http://omlc.ogi.edu/spectra/PhotochemCAD), yielding f = 4.32E-9 * > INT[eps(nu)dnu] = 2.73. For the extremely strong band with maximum at 44800 > cm-1 and eps = 1.1E6, integration yields f > 7. > > > > Yours, Jens >--< > > > > > > ------------------------------------------------------ > > JENS SPANGET-LARSEN Office: +45 4674 2710 > > Dept. of Science (18.1) Fax: +45 4674 3011 > > Roskilde University Mobile: +45 2320 6246 > > P.O.Box 260 E-Mail: spanget_-_ruc.dk > > DK-4000 Roskilde, Denmark http://www.ruc.dk/~spanget > > ------------------------------------------------------ > > > > *From:* owner-chemistry+spanget==ruc.dk_-_ccl.net [mailto: > owner-chemistry+spanget==ruc.dk_-_ccl.net] *On Behalf Of *Hao-Bo Guo > guohaobo()gmail.com > *Sent:* 11. december 2013 19:03 > *To:* Jens Spanget-Larsen > *Subject:* CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high > > > > "the sum of the oscillator strengths from one sub-state to all other > states is equal to the total number of electrons N" > > My understanding is the sum of oscillator strengths equals to the number > of electron(s) excited, which is 1, for single electron excitation > calculations w/ TDDFT. > > Hao-Bo > > > > On Wed, Dec 11, 2013 at 10:03 AM, Jens Spanget-Larsen spanget]=[ruc.dk < > owner-chemistry!=cl.net> wrote: > > > Dear Micaela, > > According to "IUPAC Glossary of terms used in photochemistry, 3rd Edition, > 2005", the oscillator strength f is defined as: > > f = (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2 > > where m is the mass of the electron, c is the velocity of light, nu is the > wavenumber, e is the elementary charge, and h is the Planck constant. G is > the degeneracy of the final state, and M is the transition moment vector. > Formally, there is no upper limit to nu and the length of M, and there is > thus no reason why the magnitude of f should not increase unity (however, > according to the Thomas-Reiche-Kuhn sum rule, the sum of the oscillator > strengths from one sub-state to all other states is equal to the total > number of electrons N). > > Yors, Jens >--< > > P.S. Experimentally, f is determined by integration over the entire > absorption band-width of the molar decadic absorption coefficient eps(nu), > f = INT[eps(nu)dnu]. > > ------------------------------------------------------ > JENS SPANGET-LARSEN Office: +45 4674 2710 > Dept. of Science (18.1) Fax: +45 4674 3011 > Roskilde University Mobile: +45 2320 6246 > P.O.Box 260 E-Mail: spanget#,#ruc.dk #,#ruc.dk> > DK-4000 Roskilde, Denmark http://www.ruc.dk/~spanget > ------------------------------------------------------ > > > From: owner-chemistry+spanget==ruc.dk#,#ccl.net[mailto: > owner-chemistry+spanget==ruc.dk#,#ccl.net ] On > Behalf Of Micaela Matta micaela.matta2+/-unibo.it > Sent: 11. december 2013 09:29 > To: Jens Spanget-Larsen > Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high > > Dear Jens, > I thught it to be unreasonable because oscillator strength must be less or > equal than one, and this had never happened to me before. > Thank you very much to all of you! > Micaela > > 2013/12/11 Somananda Sanyal somananda.sanyal]|[gmail.com > > > Dear Micaela, > The oscillator strength you are getting using CAM-B3LYp, or for that > matter many other functionals that I too have checked with, such f>1 > results come. > As far as I know, it is because of the fact that the oscillator strengths > are not normalized, so that is why they come as greater than 1 value. > > Thanks and regards, > Somanand Sanyal > > > > > > > > > > ***************** > Regards, > Somananda Sanyal. > Theoretical Sciences Unit, > JNCASR, Bangalore. > > On Wed, Dec 11, 2013 at 4:23 AM, Jens Spanget-Larsen spanget,+,ruc.dk< > http://ruc.dk> > > wrote: > > Sent to CCL by: Jens Spanget-Larsen [spanget[]ruc.dk] > > Dear Micaela, > why do you think that an oscillator strength f = 2.7 is unphysical? This > is certainly a large value, but it is not necessarily unreasonable. With > TD-PBE1PBE/6-31+G*, we obtained f = 2.2 for the first optically allowed > electronic transition in the D2d conformation of diphenyldiacetylene, see > Thulstrup et al., PCCP 13, 16168-16174 (2011). > Jens >--< > > ------------------------------------------------------ > JENS SPANGET-LARSEN Office: +45 4674 2710< > tel:%2B45%204674%202710 <%2B45%204674%202710>> > Dept. of Science (18.1) Fax: +45 4674 3011< > tel:%2B45%204674%203011 <%2B45%204674%203011>> > Roskilde University Mobile: +45 2320 6246< > tel:%2B45%202320%206246 <%2B45%202320%206246>> > P.O.Box 260 E-Mail: spanget{=}ruc.dk > DK-4000 Roskilde, Denmark http://www.ruc.dk/~spanget > ------------------------------------------------------ > > ________________________________________ > Fra: owner-chemistry+spanget==ruc.dk{=}ccl.net< > http://ccl.net> [owner-chemistry+spanget==ruc.dk{=}ccl.net< > http://ccl.net>] på vegne af micaela matta micaela.matta2 .. unibo.it > [owner-chemistry{=}ccl.net] > Sendt: 10. december 2013 17:05 > Til: Jens Spanget-Larsen > Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high > > Sent to CCL by: "micaela matta" [micaela.matta2 .. unibo.it< > http://unibo.it>] > Dear CCL suscribers, > > I am running TD-DFT calculations on an organic molecule at level > CAM-BLYP/6- > 311G*. The first excited state has the correct energy compared to > experimental > results, but I obtained an unphysical f=2.7206!! How can I make sense of > this > result? > Thanks > > Micaelahttp:// > www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt E-mail to subscribers: CHEMISTRY],[ccl.net or > use:E-mail to administrators: CHEMISTRY-REQUEST],[ccl.net CHEMISTRY-REQUEST],[ccl.net> or usehttp:// > www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt--_000_A94E15A372E6194CA8719D62642F674463C57C16MBX3adrucdk_ > Content-Type: > text/html; charset"us-ascii" > Content-Transfer-Encoding: quoted-printable > > xmlns:o="urn:schemas-microsoft-com:office:office" > xmlns:w="urn:schemas-microsoft-com:office:word" xmlns:m=" > http://schemas.microsoft.com/office/2004/12/omml" xmlns=" > http://www.w3.org/TR/REC-html40"> > > > > > > >
>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D"> 

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">Dear Micaela,

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D"> 

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">According to “IUPAC Glossary of terms used > in photochemistry, 3rd Edition, 2005”, the oscillator strength f is > defined as:

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D"> 

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">f = (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2 >

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D"> 

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">where m is the mass of the electron, c is the > velocity of light, nu is the wavenumber, e is the elementary charge, and h > is the Planck constant. G is the > degeneracy of the final state, and M is the transition moment vector. > Formally, there is no upper limit to nu and the length of M, and there is > thus no reason why the magnitude of f should not increase unity (however, > according to the Thomas-Reiche-Kuhn sum > rule, the sum of the oscillator strengths from one sub-state to all other > states is equal to the total number of electrons N).

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D"> 

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">Yors, Jens >--<

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D"> 

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">P.S. Experimentally, f is determined by > integration over the entire absorption band-width of the molar decadic > absorption coefficient eps(nu), f = INT[eps(nu)dnu].

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D"> 

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style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">  > style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">------------------------------------------------------

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">  JENS > SPANGET-LARSEN         > Office:      +45 4674 > 2710

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">  Dept. of Science > (18.1)     > Fax:         +45 4674 > 3011

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">  Roskilde > University         > Mobile:      +45 2320 > 6246

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">  P.O.Box > 260                 > E-Mail:     > spanget#,#ruc.dk >

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">  > DK-4000 Roskilde, Denmark   > http://www.ruc.dk/~spanget >

>

style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">  > style="font-size:10.0pt;font-family:"Courier > New";color:#1F497D">------------------------------------------------------

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style="font-size:10.0pt;font-family:"Tahoma","sans-serif"">From: lang="EN-US" > style="font-size:10.0pt;font-family:"Tahoma","sans-serif""> > owner-chemistry+spanget==ruc.dk#,#ccl.net [mailto: > owner-chemistry+spanget==ruc.dk#,#ccl.net ] > On Behalf Of Micaela Matta micaela.matta2+/-unibo.it
> Sent: 11. december 2013 09:29
> To: Jens Spanget-Larsen
> Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too > high

>

 

>
>
>
>
>

Dear Jens,

>
>

I thught it to be unreasonable because oscillator > strength must be less or equal than one, and this had never happened to me > before. >

>
>

Thank you very much to all of you!

>
>

Micaela

>
>

 

>
>

2013/12/11 Somananda Sanyal somananda.sanyal]|[ href="http://gmail.com">gmail.com <owner-chemistry..ccl.net > >

>
>

Dear Micaela,

>
>

    The oscillator strength you are getting > using CAM-B3LYp, or for that matter many other functionals that I too have > checked with, such f>1 results come.

>
>
>

As far as I know, it is because of the fact that the > oscillator strengths are not normalized, so that is why they come as > greater than 1 value.

>
>
>

 

>
>
>

Thanks and regards,

>
>
>

Somanand Sanyal

>
>
>
>


>

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style="color:silver">*****************

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style="font-family:"Tahoma","sans-serif";color:#999999">Regards,

>
>
>

style="font-family:"Tahoma","sans-serif";color:#999999">Somananda > Sanyal.
> Theoretical Sciences Unit,
> JNCASR, Bangalore.

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On Wed, Dec 11, 2013 at 4:23 AM, Jens Spanget-Larsen > spanget,+,ruc.dk < href="mailto:owner-chemistry],[ccl.net" target="_blank">owner-chemistry],[ > ccl.net> wrote:

>
>
>
>
>
>


> Sent to CCL by: Jens Spanget-Larsen [spanget[] target="_blank">ruc.dk]
>
> Dear Micaela,
> why do you think that an oscillator strength f = 2.7 is unphysical? This > is certainly a large value, but it is not necessarily unreasonable. With > TD-PBE1PBE/6-31+G*, we obtained f = 2.2  for the first optically > allowed electronic transition in the D2d conformation > of diphenyldiacetylene, see Thulstrup et al., PCCP 13, 16168-16174 > (2011).
> Jens >--<
>
>   ------------------------------------------------------
>   JENS SPANGET-LARSEN         Office:   >     target="_blank">+45 4674 2710
>   Dept. of Science (18.1)     Fax:       >   target="_blank"> > +45 4674 3011
>   Roskilde University         Mobile:   >     target="_blank">+45 2320 6246
>   P.O.Box 260                 > E-Mail:     spanget{=} > ruc.dk
>   DK-4000 Roskilde, Denmark   > http://www.ruc.dk/~spanget
>   ------------------------------------------------------
>
> ________________________________________
> Fra: owner-chemistry+spanget== > ruc.dk{=}ccl.net > [owner-chemistry+spanget== > ruc.dk{=}ccl.net] > p&#229; vegne af micaela matta micaela.matta2 .. > unibo.it [owner-chemistry{=} > ccl.net]
> Sendt: 10. december 2013 17:05
> Til: Jens Spanget-Larsen
> Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high
>
> Sent to CCL by: "micaela  matta" [micaela.matta2 .. href="http://unibo.it" target="_blank"> > unibo.it]
> Dear CCL suscribers,
>
> I am running TD-DFT calculations on an organic molecule at level > CAM-BLYP/6-
> 311G*. The first excited state has the correct energy compared to > experimental
> results, but I obtained an unphysical f=2.7206!! How can I make sense of > this
> result?
> Thanks
>
> Micaelahttp:// target="_blank"> > www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt >
>
>

>
>
>

E-mail to subscribers: > CHEMISTRY],[ccl.net or use:
>      
>
> E-mail to administrators: target="_blank"> > CHEMISTRY-REQUEST],[ccl.net or use

> > >
>
>

 

>
>
>

 

>
>
>
> > > > > > > -- > > Hao-Bo Guo > > BCMB Department > > University of Tennessee Knoxville > > Plant Systems Biology Group > > Oak Ridge National Laboratory > > 865-803-4432; guoh1!=rnl.gov > -- Hao-Bo Guo BCMB Department University of Tennessee Knoxville Plant Systems Biology Group Oak Ridge National Laboratory 865-803-4432; guoh1*|*ornl.gov --e89a8ff1c94c02d91f04ed6cc568 Content-Type: text/html; charset=ISO-8859-1 Content-Transfer-Encoding: quoted-printable
Dear Jen,
Yeah, I've got it. I almost forgot w= ithout your reply! Because this is also how I generated the experimental ba= nd spectra from the line spectra calculated by TDDFT, eg., using Gaussian e= xpansions:
eps(nu) =3D (1/4.32E-9) * sigma[f_i * G(nu_i)]
Thank you very much!
<= /div>
Best regards, Hao-Bo

On Thu, Dec 12, 2013 at 6:20 AM, Jens Span= get-Larsen spanget%%ruc.dk = <owner-chem= istry*|*ccl.net> wrote:

=A0

Dear Micaela and others!

The f-sum rule may be stated = as follows:

=A0

The sum of all oscillator str= engths, f(0,n), from a state |0> to all other states |n> obeys the su= m rule SUMMA(n) f(0,n) =3D N

=A0

--

>=A0 f(0,n) =3D N

--

n#0

=A0

where N is the total number o= f electrons in the system (also called the Thomas-Reiche-Kuhn sum rule).=

=A0

This formulation is taken fro= m Poul Joergensen & Jens Oddershede: "Problems in quantum chemistr= y", Addison-Wesley, Massachusetts, USA, 1983. Hence, the f-value for an electronic transition is not limited to magnitudes below or= equal to unity, it may increase unity. As a matter of fact, it frequently = does. For example, the experimental oscillator strength for the first trans= ition in all-trans beta-carotene is equal to f =3D 2.7. This is the value obtained by integration over the = absorption band in hexane with maximum at 22200 cm-1 and eps =3D 139400 (http:/= /omlc.ogi.edu/spectra/PhotochemCAD), yielding f =3D 4.32E-9 * INT[eps(n= u)dnu] =3D 2.73. For the extremely strong band with maximum at 44800 cm-1 and eps =3D 1.1E6, integration yields f &g= t; 7.

=A0

Yours, Jens >--<<= /p>

=A0

=A0

=A0 -------------------------= -----------------------------

=A0 JENS SPANGET-LARSEN=A0=A0= =A0=A0=A0=A0=A0=A0 Office:=A0=A0=A0=A0=A0 +45 4674 2710<= /span>

=A0 Dept. of Science (18.1)= =A0=A0=A0=A0 Fax:=A0=A0=A0=A0=A0=A0=A0=A0 +45 4674 3011<= /span>

=A0 Roskilde University=A0=A0= =A0=A0=A0=A0=A0=A0 Mobile:=A0=A0=A0=A0=A0 +45 2320 6246<= /span>

=A0 P.O.Box 260=A0=A0=A0=A0= =A0=A0=A0=A0=A0=A0=A0=A0=A0=A0=A0=A0 E-Mail:=A0=A0=A0=A0 spanget_-_ruc.dk<= u>

=A0 DK-4000 Roskilde, Denmark=A0=A0 http://www.ruc.dk/= ~spanget

=A0 ---------------------------------------------= ---------

=A0<= /p>

From: owner-chemistry+spanget=3D=3Druc.dk_-_ccl.net [mailto:owner-chemistry+spanget= =3D=3Druc.dk_-_ccl.ne= t] On Behalf Of Hao-Bo Guo guohaobo()gmail.com
Sent: 11. december 2013 19:03
To: Jens Spanget-Larsen
Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high<= /u>

=A0

"the sum of the oscillator strengths from one s= ub-state to all other states is equal to the total number of electrons N&qu= ot;

My understanding is t= he sum of oscillator strengths equals to the number of electron(s) excited,= which is 1, for single electron excitation calculations w/ TDDFT.

Hao-Bo

=A0

On Wed, Dec 11, 2013 at 10:03 AM, Jens Spanget-Larse= n spanget]=3D[ruc.dk <owner-chemistr= y!=3Dcl.net> wrote:


Dear Micaela,

According to "IUPAC Glossary of terms used in photochemistry, 3rd Edit= ion, 2005", the oscillator strength f is defined as:

f =3D (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2

where m is the mass of the electron, c is the velocity of light, nu is the = wavenumber, e is the elementary charge, and h is the Planck constant. G is = the degeneracy of the final state, and M is the transition moment vector. F= ormally, there is no upper limit to nu and the length of M, and there is thus no reason why the magnitude o= f f should not increase unity (however, according to the Thomas-Reiche-Kuhn= sum rule, the sum of the oscillator strengths from one sub-state to all ot= her states is equal to the total number of electrons N).

Yors, Jens >--<

P.S. Experimentally, f is determined by integration over the entire absorpt= ion band-width of the molar decadic absorption coefficient eps(nu), f =3D I= NT[eps(nu)dnu].

=A0 ------------------------------------------------------
=A0 JENS SPANGET-LARSEN =A0 =A0 =A0 =A0 Office: =A0 =A0 =A0+45 4674 2710
=A0 Dept. of Science (18.1) =A0 =A0 Fax: =A0 =A0 =A0 =A0 +45 4674 3011=
=A0 Roskilde University =A0 =A0 =A0 =A0 Mobile: =A0 =A0 =A0+45 2320 6246
=A0 P.O.Box 260 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 E-Mail: =A0 =A0 spanget#,#<= a href=3D"http://ruc.dk" target=3D"_blank">ruc.dk<mailto:spanget#,#ruc.dk>
=A0 DK-4000 Roskilde, Denmark =A0 http://www.ruc.dk/~spanget
=A0 ------------------------------------------------------

> From: owner-chemistry+spanget=3D=3Druc.dk#,#ccl.net [mailto:owner-chemistry+spanget=3D=3Druc.dk#,#ccl.net] O= n Behalf Of Micaela Matta micaela.matta2+/-unibo.it
Sent: 11. december 2013 09:29
To: Jens Spanget-Larsen
Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high

Dear Jens,
I thught it to be unreasonable because oscillator strength must be less or = equal than one, and this had never happened to me before.
Thank you very much to all of you!
Micaela

2013/12/11 Somananda Sanyal somananda.sanyal]|[gmail.com<http://gmail.com> <owner-chemistry..ccl.net<mailto:owner-chemistry..ccl.net>>
Dear Micaela,
=A0 =A0 The oscillator strength you are getting using CAM-B3LYp, or for tha= t matter many other functionals that I too have checked with, such f>1 r= esults come.
As far as I know, it is because of the fact that the oscillator strengths a= re not normalized, so that is why they come as greater than 1 value.

Thanks and regards,
Somanand Sanyal









*****************
Regards,
Somananda Sanyal.
Theoretical Sciences Unit,
JNCASR, Bangalore.

On Wed, Dec 11, 2013 at 4:23 AM, Jens Spanget-Larsen spanget,+,ruc.dk<http://ruc.dk> <owner-chemistry],[ccl.net<mailto:owner-chemistry],[ccl.net>> wrote:

Sent to CCL by: Jens Spanget-Larsen [spanget[]ruc.dk<ht= tp://ruc.dk>]

Dear Micaela,
why do you think that an oscillator strength f =3D 2.7 is unphysical? This = is certainly a large value, but it is not necessarily unreasonable. With TD= -PBE1PBE/6-31+G*, we obtained f =3D 2.2 =A0for the first optically allowed = electronic transition in the D2d conformation of diphenyldiacetylene, see Thulstrup et al., PCCP 13, 16168-16174 (2011).=
Jens >--<

=A0 ------------------------------------------------------
=A0 JENS SPANGET-LARSEN =A0 =A0 =A0 =A0 Office: =A0 =A0 =A0+45 4674 2710<tel:%2B45%20467= 4%202710>
=A0 Dept. of Science (18.1) =A0 =A0 Fax: =A0 =A0 =A0 =A0 +45 4674 3011= <tel:%2B45%204674%= 203011>
=A0 Roskilde University =A0 =A0 =A0 =A0 Mobile: =A0 =A0 =A0+45 2320 6246<tel:%2B45%20232= 0%206246>
=A0 P.O.Box 260 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 E-Mail: =A0 =A0 spanget{=3D= }ruc.dk<http://ruc.dk>
=A0 DK-4000 Roskilde, Denmark =A0 http://www.ruc.dk/~spanget
=A0 ------------------------------------------------------

________________________________________
Fra: owner-chemistry+spanget=3D=3Druc.dk<http://ruc.dk<= /a>>{=3D}ccl.net<http://ccl.net> [owner-che= mistry+spanget=3D=3Druc.dk&= lt;http://ruc.dk>{=3D}ccl.net<http://ccl.net>] p&#229; vegne af micaela matta micaela.matta2 .. unibo.it<http://unibo.= it> [owner-chemistry{=3D}ccl.net<http://ccl.ne= t>]
Sendt: 10. december 2013 17:05
Til: Jens Spanget-Larsen
Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high

Sent to CCL by: "micaela =A0matta" [micaela.matta2 .. unibo.it<http://unibo.= it>]
Dear CCL suscribers,

I am running TD-DFT calculations on an organic molecule at level CAM-BLYP/6= -
311G*. The first excited state has the correct energy compared to experimen= tal
results, but I obtained an unphysical f=3D2.7206!! How can I make sense of = this
result?
Thanks

Micaelahttp://www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/c= hemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt<http://www.= ccl.net/cgi-bin/ccl/send_ccl_messagehttp:/www.ccl.net/chemistry/sub_unsub.s= htmlhttp:/www.ccl.net/spammers.txt>


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<div class=3D"WordSection1">
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">Dear Micaela,<o:p></o:p></span></= p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">According to &#8220;IUPAC Glossary of terms used i= n photochemistry, 3rd Edition, 2005&#8221;, the oscillator strength f i= s defined as:<o:p></o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span style=3D"font-size:10.= 0pt;font-family:&quot;Courier New&quot;;color:#1F497D">f = =3D (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2
<o:p></o:p></span></p>
<p class=3D"MsoNormal"><span style=3D"font-size:10.= 0pt;font-family:&quot;Courier New&quot;;color:#1F497D"><= o:p>&nbsp;</o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">where m is the mass of the electron, c is the velocity= of light, nu is the wavenumber, e is the elementary charge, and h is the P= lanck constant. G is the
=A0degeneracy of the final state, and M is the transition moment vector. Fo= rmally, there is no upper limit to nu and the length of M, and there is thu= s no reason why the magnitude of f should not increase unity (however, acco= rding to the Thomas-Reiche-Kuhn sum
=A0rule, the sum of the oscillator strengths from one sub-state to all othe= r states is equal to the total number of electrons N).<o:p></o:p&g= t;</span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">Yors, Jens &gt;--&lt;<o:p></o:p>&l= t;/span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">P.S. Experimentally, f is determined by integration ov= er the entire absorption band-width of the molar decadic absorption coeffic= ient eps(nu), f =3D INT[eps(nu)dnu].<o:p></o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp;
</span><span lang=3D"EN-GB" style=3D"font-size:10.0= pt;font-family:&quot;Courier New&quot;;color:#1F497D">-----= -------------------------------------------------<o:p></o:p><= ;/span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; JENS SPANGET-LARSEN&nbsp;&nbsp;&= ;nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Office:&nbsp;&= amp;nbsp;&nbsp;&nbsp;&nbsp; &#43;45 4674 2710<o:p><= ;/o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; Dept. of Science (18.1)&nbsp;&nbsp;= &nbsp;&nbsp; Fax:&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;= &nbsp;&nbsp;&nbsp; &#43;45 4674 3011<o:p></o:p>= </span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; Roskilde University&nbsp;&nbsp;&= ;nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Mobile:&nbsp;&= amp;nbsp;&nbsp;&nbsp;&nbsp; &#43;45 2320 6246<o:p><= ;/o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; P.O.Box 260&nbsp;&nbsp;&nbsp;&a= mp;nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nb= sp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; E-Mail:&nbsp;&= ;nbsp;&nbsp;&nbsp;
<a href=3D"mailto:span= get#,#ruc.dk">s= panget#,#ruc.dk</a>&l= t;o:p></o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp;
</span><span style=3D"font-size:10.0pt;font-family:&quot;= Courier New&quot;;color:#1F497D">DK-4000 Roskilde, Denmark&= nbsp;&nbsp;
<a href=3D"http://www.ruc.dk/~spanget">http://www.ruc.dk/~spanget</a><o:p>&= lt;/o:p></span></p>
<p class=3D"MsoNormal"><span style=3D"font-size:10.= 0pt;font-family:&quot;Courier New&quot;;color:#1F497D">&= ;nbsp;
</span><span lang=3D"EN-GB" style=3D"font-size:10.0= pt;font-family:&quot;Courier New&quot;;color:#1F497D">-----= -------------------------------------------------<o:p></o:p><= ;/span></p>
<p class=3D"MsoNormal"><span style=3D"font-size:11.= 0pt;font-family:&quot;Calibri&quot;,&quot;sans-serif&quot;;= color:#1F497D"><o:p>&nbsp;</o:p></span></p= >
<p class=3D"MsoNormal"><b><span lang=3D"EN-US= " style=3D"font-size:10.0pt;font-family:&quot;Tahoma&quot= ;,&quot;sans-serif&quot;">From:</span></b><s= pan lang=3D"EN-US" style=3D"font-size:10.0pt;font-family:&am= p;quot;Tahoma&quot;,&quot;sans-serif&quot;"> owner-chem= istry&#43;spanget=3D=3Druc.dk#,#ccl.net [mailto:owner-chem= istry&#43;spanget=3D=3Druc.dk#,#ccl.net]
<b>On Behalf Of </b>Micaela Matta micaela.matta2&#43;/-unibo.it<br>
<b>Sent:</b> 11. december 2013 09:29<br>
<b>To:</b> Jens Spanget-Larsen<br>
<b>Subject:</b> CCL: SV: TDDFT (CAM-B3LYP) oscillator strength = too high<o:p></o:p></span></p>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
<div>
<div>
<div>
<div>
<p class=3D"MsoNormal">Dear Jens,<o:p></o:p><= ;/p>
</div>
<p class=3D"MsoNormal">I thught it to be unreasonable becau= se oscillator strength must be less or equal than one, and this had never h= appened to me before.
<o:p></o:p></p>
</div>
<p class=3D"MsoNormal">Thank you very much to all of you!&l= t;o:p></o:p></p>
</div>
<p class=3D"MsoNormal">Micaela<o:p></o:p></p= >
<div>
<p class=3D"MsoNormal" style=3D"margin-bottom:12.0pt"= ;><o:p>&nbsp;</o:p></p>
<div>
<p class=3D"MsoNormal">2013/12/11 Somananda Sanyal somanand= a.sanyal]|[<a href=3D"http://gmail.com">gmail.com</a> &lt;<a href=3D"mailto:owner-chemistry..ccl.net" target=3D"_blank">owner-chemistry..ccl.net</a>&gt;<o:p></o:p><= /p>
<div>
<p class=3D"MsoNormal">Dear&nbsp;Micaela,<o:p><= ;/o:p></p>
<div>
<p class=3D"MsoNormal">&nbsp; &nbsp; The oscillator= strength you are getting using CAM-B3LYp, or for that matter many other fu= nctionals that I too have checked with, such f&gt;1 results come.<o:= p></o:p></p>
</div>
<div>
<p class=3D"MsoNormal">As far as I know, it is because of t= he fact that the oscillator strengths are not normalized, so that is why th= ey come as greater than 1 value.<o:p></o:p></p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal">Thanks and regards,<o:p></o= :p></p>
</div>
<div>
<p class=3D"MsoNormal">Somanand Sanyal<o:p></o:p&g= t;</p>
</div>
</div>
<div>
<p class=3D"MsoNormal"><br clear=3D"all"> <o:p></o:p></p>
<div>
<div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal"><span style=3D"color:silver&= quot;>*****************</span><o:p></o:p></p> </div>
<div>
<p class=3D"MsoNormal"><span style=3D"font-family:&= amp;quot;Tahoma&quot;,&quot;sans-serif&quot;;color:#999999"= ;>Regards,</span><o:p></o:p></p>
</div>
<div>
<p class=3D"MsoNormal"><span style=3D"font-family:&= amp;quot;Tahoma&quot;,&quot;sans-serif&quot;;color:#999999"= ;>Somananda Sanyal.<br>
Theoretical Sciences Unit,<br>
JNCASR, Bangalore.</span><o:p></o:p></p>
</div>
</div>
</div>
<p class=3D"MsoNormal" style=3D"margin-bottom:12.0pt"= ;><o:p>&nbsp;</o:p></p>
<div>
<div>
<div>
<p class=3D"MsoNormal">On Wed, Dec 11, 2013 at 4:23 AM, Jen= s Spanget-Larsen spanget,&#43;,<a href=3D"http://ruc.dk" target=3D"_blank"&= gt;ruc.dk</a> &lt= ;<a href=3D"mailto:owner-chemistry],[ccl= .net" target=3D"_blank">owner-chemistry],[ccl.net</a>&gt; wrote:<o:p></o:p= ></p>
</div>
</div>
<blockquote style=3D"border:none;border-left:solid #CCCCCC 1.0pt;pa= dding:0cm 0cm 0cm 6.0pt;margin-left:4.8pt;margin-right:0cm">
<div>
<div>
<p class=3D"MsoNormal"><br>
Sent to CCL by: Jens Spanget-Larsen [spanget[]<a href=3D"http://ruc.dk" target=3D"_b= lank">ruc.dk</a&= gt;]<br>
<br>
Dear Micaela,<br>
why do you think that an oscillator strength f =3D 2.7 is unphysical? This = is certainly a large value, but it is not necessarily unreasonable. With TD= -PBE1PBE/6-31&#43;G*, we obtained f =3D 2.2 &nbsp;for the first opt= ically allowed electronic transition in the D2d conformation
=A0of diphenyldiacetylene, see Thulstrup et al., PCCP 13, 16168-16174 (2011= ).<br>
Jens &gt;--&lt;<br>
<br>
&nbsp; ------------------------------------------------------<br>=
&nbsp; JENS SPANGET-LARSEN &nbsp; &nbsp; &nbsp; &nbsp; = Office: &nbsp; &nbsp; &nbsp;<a href=3D"tel:%2B45%204674%202710" tar= get=3D"_blank">&#43;45 4674 2710</a><br>
&nbsp; Dept. of Science (18.1) &nbsp; &nbsp; Fax: &nbsp; &a= mp;nbsp; &nbsp; &nbsp; <a href=3D"tel:%2B45%204674%203011" target=3D&qu= ot;_blank">
&#43;45 4674 3011</a><br>
&nbsp; Roskilde University &nbsp; &nbsp; &nbsp; &nbsp; = Mobile: &nbsp; &nbsp; &nbsp;<a href=3D"tel:%2B45%202320%206246" tar= get=3D"_blank">&#43;45 2320 6246</a><br>
&nbsp; P.O.Box 260 &nbsp; &nbsp; &nbsp; &nbsp; &nbs= p; &nbsp; &nbsp; &nbsp; E-Mail: &nbsp; &nbsp; spanget{= =3D}<a href=3D"http://r= uc.dk" target=3D"_blank">ruc.dk</a><br>
&nbsp; DK-4000 Roskilde, Denmark &nbsp; <a href=3D"http://www.ruc.dk/~spange= t" target=3D"_blank">
http://www.ruc.dk/= ~spanget</a><br>
&nbsp; ------------------------------------------------------<br>=
<br>
________________________________________<br>
Fra: owner-chemistry&#43;spanget=3D=3D<a href=3D"http://ruc.dk" target=3D"_blank= ">ruc.dk</a>{= =3D}<a href=3D"http://= ccl.net" target=3D"_blank">ccl.net</a> [owner-chemistry&#43;spanget=3D=3D<a href=3D"http://ruc.dk" target=3D"_blank&qu= ot;>ruc.dk</a>{=3D= }<a href=3D"http://ccl= .net" target=3D"_blank">ccl.net</a>]
=A0p&amp;#229; vegne af micaela matta micaela.matta2 .. <a href=3D&q= uot;http://unibo.it"= target=3D"_blank">
unibo.it</a> [owner= -chemistry{=3D}<a href=3D"http://ccl.net" target=3D"_blank">ccl.net</a>]<br>
Sendt: 10. december 2013 17:05<br>
Til: Jens Spanget-Larsen<br>
Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high<br>
<br>
Sent to CCL by: &quot;micaela &nbsp;matta&quot; [micaela.matta2= .. <a href=3D"http:/= /unibo.it" target=3D"_blank">
unibo.it</a>]<br= >
Dear CCL suscribers,<br>
<br>
I am running TD-DFT calculations on an organic molecule at level CAM-BLYP/6= -<br>
311G*. The first excited state has the correct energy compared to experimen= tal<br>
results, but I obtained an unphysical f=3D2.7206!! How can I make sense of = this<br>
result?<br>
Thanks<br>
<br>
Micaelahttp://<a href=3D"http://www.ccl.net/cgi-bin/ccl/send_ccl_m= essagehttp:/www.ccl.net/chemistry/sub_unsub.shtmlhttp:/www.ccl.net/spammers= .txt" target=3D"_blank">www.ccl.net/cgi-bin/ccl/send_ccl_messageht= tp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt</a><br>
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--

Hao-Bo Guo

BCMB Department

University of Tennessee Knoxville

Plant Systems Biology Group

Oak Ridge National Laboratory

865-803-4432; guoh1!=3Drnl.gov




--
<= div>
Hao-Bo Guo
BCMB Department
= University of Tennessee Knoxville
Plant Systems Biology Group
Oak Ridge National Laboratory
865-803-4432; guoh1*|*ornl.gov
--e89a8ff1c94c02d91f04ed6cc568-- From owner-chemistry@ccl.net Fri Dec 13 13:31:00 2013 From: "Hao-Bo Guo guohaobo{=}gmail.com" To: CCL Subject: CCL:G: SV: TDDFT (CAM-B3LYP) oscillator strength too high Message-Id: <-49447-131213112041-20566-/JfyXly3izeHuSu+D+8JXA() server.ccl.net> X-Original-From: Hao-Bo Guo Content-Type: multipart/alternative; boundary=001a11365370e7155704ed6cd651 Date: Fri, 13 Dec 2013 11:20:24 -0500 MIME-Version: 1.0 Sent to CCL by: Hao-Bo Guo [guohaobo!A!gmail.com] --001a11365370e7155704ed6cd651 Content-Type: text/plain; charset=ISO-8859-1 Sorry, it must be the Gaussian expansion on excitation energy (E) then traversed to wavelength (nu); but it is not on the wavelength directly. On Fri, Dec 13, 2013 at 11:15 AM, Hao-Bo Guo wrote: > Dear Jen, > Yeah, I've got it. I almost forgot without your reply! Because this is > also how I generated the experimental band spectra from the line spectra > calculated by TDDFT, eg., using Gaussian expansions: > eps(nu) = (1/4.32E-9) * sigma[f_i * G(nu_i)] > Thank you very much! > Best regards, Hao-Bo > > > On Thu, Dec 12, 2013 at 6:20 AM, Jens Spanget-Larsen spanget%%ruc.dk < > owner-chemistry-,-ccl.net> wrote: > >> >> >> Dear Micaela and others! >> >> The f-sum rule may be stated as follows: >> >> >> >> The sum of all oscillator strengths, f(0,n), from a state |0> to all >> other states |n> obeys the sum rule SUMMA(n) f(0,n) = N >> >> >> >> -- >> >> > f(0,n) = N >> >> -- >> >> n#0 >> >> >> >> where N is the total number of electrons in the system (also called the >> Thomas-Reiche-Kuhn sum rule). >> >> >> >> This formulation is taken from Poul Joergensen & Jens Oddershede: >> "Problems in quantum chemistry", Addison-Wesley, Massachusetts, USA, 1983. >> Hence, the f-value for an electronic transition is not limited to >> magnitudes below or equal to unity, it may increase unity. As a matter of >> fact, it frequently does. For example, the experimental oscillator strength >> for the first transition in all-trans beta-carotene is equal to f = 2.7. >> This is the value obtained by integration over the absorption band in >> hexane with maximum at 22200 cm-1 and eps = 139400 ( >> http://omlc.ogi.edu/spectra/PhotochemCAD), yielding f = 4.32E-9 * >> INT[eps(nu)dnu] = 2.73. For the extremely strong band with maximum at 44800 >> cm-1 and eps = 1.1E6, integration yields f > 7. >> >> >> >> Yours, Jens >--< >> >> >> >> >> >> ------------------------------------------------------ >> >> JENS SPANGET-LARSEN Office: +45 4674 2710 >> >> Dept. of Science (18.1) Fax: +45 4674 3011 >> >> Roskilde University Mobile: +45 2320 6246 >> >> P.O.Box 260 E-Mail: spanget_-_ruc.dk >> >> DK-4000 Roskilde, Denmark http://www.ruc.dk/~spanget >> >> ------------------------------------------------------ >> >> >> >> *From:* owner-chemistry+spanget==ruc.dk_-_ccl.net [mailto: >> owner-chemistry+spanget==ruc.dk_-_ccl.net] *On Behalf Of *Hao-Bo Guo >> guohaobo()gmail.com >> *Sent:* 11. december 2013 19:03 >> *To:* Jens Spanget-Larsen >> *Subject:* CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high >> >> >> >> "the sum of the oscillator strengths from one sub-state to all other >> states is equal to the total number of electrons N" >> >> My understanding is the sum of oscillator strengths equals to the number >> of electron(s) excited, which is 1, for single electron excitation >> calculations w/ TDDFT. >> >> Hao-Bo >> >> >> >> On Wed, Dec 11, 2013 at 10:03 AM, Jens Spanget-Larsen spanget]=[ruc.dk < >> owner-chemistry!=cl.net> wrote: >> >> >> Dear Micaela, >> >> According to "IUPAC Glossary of terms used in photochemistry, 3rd >> Edition, 2005", the oscillator strength f is defined as: >> >> f = (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2 >> >> where m is the mass of the electron, c is the velocity of light, nu is >> the wavenumber, e is the elementary charge, and h is the Planck constant. G >> is the degeneracy of the final state, and M is the transition moment >> vector. Formally, there is no upper limit to nu and the length of M, and >> there is thus no reason why the magnitude of f should not increase unity >> (however, according to the Thomas-Reiche-Kuhn sum rule, the sum of the >> oscillator strengths from one sub-state to all other states is equal to the >> total number of electrons N). >> >> Yors, Jens >--< >> >> P.S. Experimentally, f is determined by integration over the entire >> absorption band-width of the molar decadic absorption coefficient eps(nu), >> f = INT[eps(nu)dnu]. >> >> ------------------------------------------------------ >> JENS SPANGET-LARSEN Office: +45 4674 2710 >> Dept. of Science (18.1) Fax: +45 4674 3011 >> Roskilde University Mobile: +45 2320 6246 >> P.O.Box 260 E-Mail: spanget#,#ruc.dk> #,#ruc.dk> >> DK-4000 Roskilde, Denmark http://www.ruc.dk/~spanget >> ------------------------------------------------------ >> >> > From: owner-chemistry+spanget==ruc.dk#,#ccl.net[mailto: >> owner-chemistry+spanget==ruc.dk#,#ccl.net ] >> On Behalf Of Micaela Matta micaela.matta2+/-unibo.it >> Sent: 11. december 2013 09:29 >> To: Jens Spanget-Larsen >> Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high >> >> Dear Jens, >> I thught it to be unreasonable because oscillator strength must be less >> or equal than one, and this had never happened to me before. >> Thank you very much to all of you! >> Micaela >> >> 2013/12/11 Somananda Sanyal somananda.sanyal]|[gmail.com >> > >> Dear Micaela, >> The oscillator strength you are getting using CAM-B3LYp, or for that >> matter many other functionals that I too have checked with, such f>1 >> results come. >> As far as I know, it is because of the fact that the oscillator strengths >> are not normalized, so that is why they come as greater than 1 value. >> >> Thanks and regards, >> Somanand Sanyal >> >> >> >> >> >> >> >> >> >> ***************** >> Regards, >> Somananda Sanyal. >> Theoretical Sciences Unit, >> JNCASR, Bangalore. >> >> On Wed, Dec 11, 2013 at 4:23 AM, Jens Spanget-Larsen spanget,+,ruc.dk< >> http://ruc.dk> > ccl.net>> wrote: >> >> Sent to CCL by: Jens Spanget-Larsen [spanget[]ruc.dk] >> >> Dear Micaela, >> why do you think that an oscillator strength f = 2.7 is unphysical? This >> is certainly a large value, but it is not necessarily unreasonable. With >> TD-PBE1PBE/6-31+G*, we obtained f = 2.2 for the first optically allowed >> electronic transition in the D2d conformation of diphenyldiacetylene, see >> Thulstrup et al., PCCP 13, 16168-16174 (2011). >> Jens >--< >> >> ------------------------------------------------------ >> JENS SPANGET-LARSEN Office: +45 4674 2710< >> tel:%2B45%204674%202710 <%2B45%204674%202710>> >> Dept. of Science (18.1) Fax: +45 4674 3011< >> tel:%2B45%204674%203011 <%2B45%204674%203011>> >> Roskilde University Mobile: +45 2320 6246< >> tel:%2B45%202320%206246 <%2B45%202320%206246>> >> P.O.Box 260 E-Mail: spanget{=}ruc.dk >> DK-4000 Roskilde, Denmark http://www.ruc.dk/~spanget >> ------------------------------------------------------ >> >> ________________________________________ >> Fra: owner-chemistry+spanget==ruc.dk{=}ccl.net< >> http://ccl.net> [owner-chemistry+spanget==ruc.dk{=}ccl.net >> ] på vegne af micaela matta micaela.matta2 .. >> unibo.it [owner-chemistry{=}ccl.net] >> Sendt: 10. december 2013 17:05 >> Til: Jens Spanget-Larsen >> Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high >> >> Sent to CCL by: "micaela matta" [micaela.matta2 .. unibo.it< >> http://unibo.it>] >> Dear CCL suscribers, >> >> I am running TD-DFT calculations on an organic molecule at level >> CAM-BLYP/6- >> 311G*. The first excited state has the correct energy compared to >> experimental >> results, but I obtained an unphysical f=2.7206!! How can I make sense of >> this >> result? >> Thanks >> >> Micaelahttp:// >> www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt> E-mail to subscribers: CHEMISTRY],[ccl.net >> or use:E-mail to administrators: CHEMISTRY-REQUEST],[ccl.net> CHEMISTRY-REQUEST],[ccl.net> or usehttp:// >> www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt--_000_A94E15A372E6194CA8719D62642F674463C57C16MBX3adrucdk_ >> Content-Type: >> text/html; charset"us-ascii" >> Content-Transfer-Encoding: quoted-printable >> >> > xmlns:o="urn:schemas-microsoft-com:office:office" >> xmlns:w="urn:schemas-microsoft-com:office:word" xmlns:m=" >> http://schemas.microsoft.com/office/2004/12/omml" xmlns=" >> http://www.w3.org/TR/REC-html40"> >> >> >> >> >> >> >>
>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">Dear Micaela,

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">According to “IUPAC Glossary of terms used >> in photochemistry, 3rd Edition, 2005”, the oscillator strength f is >> defined as:

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">f = (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2 >>

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">where m is the mass of the electron, c is the >> velocity of light, nu is the wavenumber, e is the elementary charge, and h >> is the Planck constant. G is the >> degeneracy of the final state, and M is the transition moment vector. >> Formally, there is no upper limit to nu and the length of M, and there is >> thus no reason why the magnitude of f should not increase unity (however, >> according to the Thomas-Reiche-Kuhn sum >> rule, the sum of the oscillator strengths from one sub-state to all >> other states is equal to the total number of electrons >> N).

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">Yors, Jens >--<

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">P.S. Experimentally, f is determined by >> integration over the entire absorption band-width of the molar decadic >> absorption coefficient eps(nu), f = INT[eps(nu)dnu].

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">  >> > style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">------------------------------------------------------

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">  JENS >> SPANGET-LARSEN         >> Office:      +45 4674 >> 2710

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">  Dept. of Science >> (18.1)     >> Fax:         +45 4674 >> 3011

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">  Roskilde >> University         >> Mobile:      +45 2320 >> 6246

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">  P.O.Box >> 260                 >> E-Mail:     >> spanget#,#ruc.dk >>

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">  >> DK-4000 Roskilde, Denmark   >> http://www.ruc.dk/~spanget >>

>>

> style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">  >> > style="font-size:10.0pt;font-family:"Courier >> New";color:#1F497D">------------------------------------------------------

>>

> style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D"> 

>>

> style="font-size:10.0pt;font-family:"Tahoma","sans-serif"">From:> lang="EN-US" >> style="font-size:10.0pt;font-family:"Tahoma","sans-serif""> >> owner-chemistry+spanget==ruc.dk#,#ccl.net [mailto: >> owner-chemistry+spanget==ruc.dk#,#ccl.net >> ] >> On Behalf Of Micaela Matta micaela.matta2+/-unibo.it
>> Sent: 11. december 2013 09:29
>> To: Jens Spanget-Larsen
>> Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too >> high

>>

 

>>
>>
>>
>>
>>

Dear Jens,

>>
>>

I thught it to be unreasonable because oscillator >> strength must be less or equal than one, and this had never happened to me >> before. >>

>>
>>

Thank you very much to all of you!

>>
>>

Micaela

>>
>>

 

>>
>>

2013/12/11 Somananda Sanyal somananda.sanyal]|[> href="http://gmail.com">gmail.com <owner-chemistry..ccl.net >> >

>>
>>

Dear Micaela,

>>
>>

    The oscillator strength you are >> getting using CAM-B3LYp, or for that matter many other functionals that I >> too have checked with, such f>1 results come.

>>
>>
>>

As far as I know, it is because of the fact that the >> oscillator strengths are not normalized, so that is why they come as >> greater than 1 value.

>>
>>
>>

 

>>
>>
>>

Thanks and regards,

>>
>>
>>

Somanand Sanyal

>>
>>
>>
>>


>>

>>
>>
>>
>>

 

>>
>>
>>

 

>>
>>
>>

 

>>
>>
>>

 

>>
>>
>>

 

>>
>>
>>

 

>>
>>
>>

 

>>
>>
>>

 

>>
>>
>>

> style="color:silver">*****************

>>
>>
>>

> style="font-family:"Tahoma","sans-serif";color:#999999">Regards,

>>
>>
>>

> style="font-family:"Tahoma","sans-serif";color:#999999">Somananda >> Sanyal.
>> Theoretical Sciences Unit,
>> JNCASR, Bangalore.

>>
>>
>>
>>

 

>>
>>
>>
>>

On Wed, Dec 11, 2013 at 4:23 AM, Jens Spanget-Larsen >> spanget,+,ruc.dk <> href="mailto:owner-chemistry],[ccl.net" >> target="_blank">owner-chemistry],[ccl.net> wrote:

>>
>>
>>
>>
>>
>>


>> Sent to CCL by: Jens Spanget-Larsen [spanget[]> target="_blank">ruc.dk]
>>
>> Dear Micaela,
>> why do you think that an oscillator strength f = 2.7 is unphysical? This >> is certainly a large value, but it is not necessarily unreasonable. With >> TD-PBE1PBE/6-31+G*, we obtained f = 2.2  for the first optically >> allowed electronic transition in the D2d conformation >> of diphenyldiacetylene, see Thulstrup et al., PCCP 13, 16168-16174 >> (2011).
>> Jens >--<
>>
>>   ------------------------------------------------------
>>   JENS SPANGET-LARSEN         Office:   >>    > target="_blank">+45 4674 2710
>>   Dept. of Science (18.1)     Fax:       >>   > target="_blank"> >> +45 4674 3011
>>   Roskilde University         Mobile:   >>    > target="_blank">+45 2320 6246
>>   P.O.Box 260               >>   E-Mail:     spanget{=}> target="_blank">ruc.dk
>>   DK-4000 Roskilde, Denmark   >> http://www.ruc.dk/~spanget
>>   ------------------------------------------------------
>>
>> ________________________________________
>> Fra: owner-chemistry+spanget==> target="_blank">ruc.dk{=} >> ccl.net [owner-chemistry+spanget==> target="_blank">ruc.dk{=} >> ccl.net] >> p&#229; vegne af micaela matta micaela.matta2 .. >> unibo.it [owner-chemistry{=} >> ccl.net]
>> Sendt: 10. december 2013 17:05
>> Til: Jens Spanget-Larsen
>> Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high
>>
>> Sent to CCL by: "micaela  matta" [micaela.matta2 .. > href="http://unibo.it" target="_blank"> >> unibo.it]
>> Dear CCL suscribers,
>>
>> I am running TD-DFT calculations on an organic molecule at level >> CAM-BLYP/6-
>> 311G*. The first excited state has the correct energy compared to >> experimental
>> results, but I obtained an unphysical f=2.7206!! How can I make sense of >> this
>> result?
>> Thanks
>>
>> Micaelahttp://> target="_blank"> >> www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt >>
>>
>>
>

>>
>>
>>

E-mail to subscribers: >> CHEMISTRY],[ccl.net or use:
>>      
>>
>> E-mail to administrators: > target="_blank"> >> CHEMISTRY-REQUEST],[ccl.net or use

>> >> >>
>>
>>

 

>>
>>
>>

 

>>
>>
>>
>> >> >> >> >> >> >> -- >> >> Hao-Bo Guo >> >> BCMB Department >> >> University of Tennessee Knoxville >> >> Plant Systems Biology Group >> >> Oak Ridge National Laboratory >> >> 865-803-4432; guoh1!=rnl.gov >> > > > > -- > Hao-Bo Guo > BCMB Department > University of Tennessee Knoxville > Plant Systems Biology Group > Oak Ridge National Laboratory > 865-803-4432; guoh1-,-ornl.gov > -- Hao-Bo Guo BCMB Department University of Tennessee Knoxville Plant Systems Biology Group Oak Ridge National Laboratory 865-803-4432; guoh1-,-ornl.gov --001a11365370e7155704ed6cd651 Content-Type: text/html; charset=ISO-8859-1 Content-Transfer-Encoding: quoted-printable
Sorry, it must be the Gaussian expansion on excitation ene= rgy (E) then traversed to wavelength (nu); but it is not on the wavelength = directly.


On Fri, Dec 13, 2013 at 11:15 AM, Hao-Bo Guo <guohaobo-,-gmail.com>= wrote:
Dear Jen,
Yeah, I've got it. I almost forgot w= ithout your reply! Because this is also how I generated the experimental ba= nd spectra from the line spectra calculated by TDDFT, eg., using Gaussian e= xpansions:
eps(nu) =3D (1/4.32E-9) * sigma[f_i * G(nu_i)]
Thank you very much!
<= /div>
Best regards, Hao-Bo


On Thu, Dec 12, 201= 3 at 6:20 AM, Jens Spanget-Larsen spanget%%ruc.dk <owner-chemistry-,-ccl.net> wrote= :

=A0

Dear Micaela and others!

The f-sum rule may be stated = as follows:

=A0

The sum of all oscillator str= engths, f(0,n), from a state |0> to all other states |n> obeys the su= m rule SUMMA(n) f(0,n) =3D N

=A0

--

>=A0 f(0,n) =3D N

--

n#0

=A0

where N is the total number o= f electrons in the system (also called the Thomas-Reiche-Kuhn sum rule).=

=A0

This formulation is taken fro= m Poul Joergensen & Jens Oddershede: "Problems in quantum chemistr= y", Addison-Wesley, Massachusetts, USA, 1983. Hence, the f-value for an electronic transition is not limited to magnitudes below or= equal to unity, it may increase unity. As a matter of fact, it frequently = does. For example, the experimental oscillator strength for the first trans= ition in all-trans beta-carotene is equal to f =3D 2.7. This is the value obtained by integration over the = absorption band in hexane with maximum at 22200 cm-1 and eps =3D 139400 (http:/= /omlc.ogi.edu/spectra/PhotochemCAD), yielding f =3D 4.32E-9 * INT[eps(n= u)dnu] =3D 2.73. For the extremely strong band with maximum at 44800 cm-1 and eps =3D 1.1E6, integration yields f &g= t; 7.

=A0

Yours, Jens >--<<= /p>

=A0

=A0

=A0 -------------------------= -----------------------------

=A0 JENS SPANGET-LARSEN=A0=A0= =A0=A0=A0=A0=A0=A0 Office:=A0=A0=A0=A0=A0 +45 4674 2710<= /span>

=A0 Dept. of Science (18.1)= =A0=A0=A0=A0 Fax:=A0=A0=A0=A0=A0=A0=A0=A0 +45 4674 3011<= /span>

=A0 Roskilde University=A0=A0= =A0=A0=A0=A0=A0=A0 Mobile:=A0=A0=A0=A0=A0 +45 2320 6246<= /span>

=A0 P.O.Box 260=A0=A0=A0=A0= =A0=A0=A0=A0=A0=A0=A0=A0=A0=A0=A0=A0 E-Mail:=A0=A0=A0=A0 spanget_-_ruc.dk<= u>

=A0 DK-4000 Roskilde, Denmark=A0=A0 http://www.ruc.dk/= ~spanget

=A0 ---------------------------------------------= ---------

=A0<= /p>

From: owner-chemistry+spanget=3D=3Druc.dk_-_ccl.net [mailto:owner-chemistry+spanget= =3D=3Druc.dk_-_ccl.ne= t] On Behalf Of Hao-Bo Guo guohaobo()gmail.com
Sent: 11. december 2013 19:03
To: Jens Spanget-Larsen
Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high<= /u>

=A0

"the sum of the oscillator strengths from one s= ub-state to all other states is equal to the total number of electrons N&qu= ot;

My understanding is t= he sum of oscillator strengths equals to the number of electron(s) excited,= which is 1, for single electron excitation calculations w/ TDDFT.

Hao-Bo

=A0

On Wed, Dec 11, 2013 at 10:03 AM, Jens Spanget-Larse= n spanget]=3D[ruc.dk <owner-chemistr= y!=3Dcl.net> wrote:


Dear Micaela,

According to "IUPAC Glossary of terms used in photochemistry, 3rd Edit= ion, 2005", the oscillator strength f is defined as:

f =3D (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2

where m is the mass of the electron, c is the velocity of light, nu is the = wavenumber, e is the elementary charge, and h is the Planck constant. G is = the degeneracy of the final state, and M is the transition moment vector. F= ormally, there is no upper limit to nu and the length of M, and there is thus no reason why the magnitude o= f f should not increase unity (however, according to the Thomas-Reiche-Kuhn= sum rule, the sum of the oscillator strengths from one sub-state to all ot= her states is equal to the total number of electrons N).

Yors, Jens >--<

P.S. Experimentally, f is determined by integration over the entire absorpt= ion band-width of the molar decadic absorption coefficient eps(nu), f =3D I= NT[eps(nu)dnu].

=A0 ------------------------------------------------------
=A0 JENS SPANGET-LARSEN =A0 =A0 =A0 =A0 Office: =A0 =A0 =A0+45 4674 2710
=A0 Dept. of Science (18.1) =A0 =A0 Fax: =A0 =A0 =A0 =A0 +45 4674 3011=
=A0 Roskilde University =A0 =A0 =A0 =A0 Mobile: =A0 =A0 =A0+45 2320 6246
=A0 P.O.Box 260 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 E-Mail: =A0 =A0 spanget#,#<= a href=3D"http://ruc.dk" target=3D"_blank">ruc.dk<mailto:spanget#,#ruc.dk>
=A0 DK-4000 Roskilde, Denmark =A0 http://www.ruc.dk/~spanget
=A0 ------------------------------------------------------

> From: owner-chemistry+spanget=3D=3Druc.dk#,#ccl.net [mailto:owner-chemistry+spanget=3D=3Druc.dk#,#ccl.net] O= n Behalf Of Micaela Matta micaela.matta2+/-unibo.it
Sent: 11. december 2013 09:29
To: Jens Spanget-Larsen
Subject: CCL: SV: TDDFT (CAM-B3LYP) oscillator strength too high

Dear Jens,
I thught it to be unreasonable because oscillator strength must be less or = equal than one, and this had never happened to me before.
Thank you very much to all of you!
Micaela

2013/12/11 Somananda Sanyal somananda.sanyal]|[gmail.com<http://gmail.com> <owner-chemistry..ccl.net<mailto:owner-chemistry..ccl.net>>
Dear Micaela,
=A0 =A0 The oscillator strength you are getting using CAM-B3LYp, or for tha= t matter many other functionals that I too have checked with, such f>1 r= esults come.
As far as I know, it is because of the fact that the oscillator strengths a= re not normalized, so that is why they come as greater than 1 value.

Thanks and regards,
Somanand Sanyal









*****************
Regards,
Somananda Sanyal.
Theoretical Sciences Unit,
JNCASR, Bangalore.

On Wed, Dec 11, 2013 at 4:23 AM, Jens Spanget-Larsen spanget,+,ruc.dk<http://ruc.dk> <owner-chemistry],[ccl.net<mailto:owner-chemistry],[ccl.net>> wrote:

Sent to CCL by: Jens Spanget-Larsen [spanget[]ruc.dk<ht= tp://ruc.dk>]

Dear Micaela,
why do you think that an oscillator strength f =3D 2.7 is unphysical? This = is certainly a large value, but it is not necessarily unreasonable. With TD= -PBE1PBE/6-31+G*, we obtained f =3D 2.2 =A0for the first optically allowed = electronic transition in the D2d conformation of diphenyldiacetylene, see Thulstrup et al., PCCP 13, 16168-16174 (2011).=
Jens >--<

=A0 ------------------------------------------------------
=A0 JENS SPANGET-LARSEN =A0 =A0 =A0 =A0 Office: =A0 =A0 =A0+45 4674 2710<tel:%2B45%20467= 4%202710>
=A0 Dept. of Science (18.1) =A0 =A0 Fax: =A0 =A0 =A0 =A0 +45 4674 3011= <tel:%2B45%204674%= 203011>
=A0 Roskilde University =A0 =A0 =A0 =A0 Mobile: =A0 =A0 =A0+45 2320 6246<tel:%2B45%20232= 0%206246>
=A0 P.O.Box 260 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 E-Mail: =A0 =A0 spanget{=3D= }ruc.dk<http://ruc.dk>
=A0 DK-4000 Roskilde, Denmark =A0 http://www.ruc.dk/~spanget
=A0 ------------------------------------------------------

________________________________________
Fra: owner-chemistry+spanget=3D=3Druc.dk<http://ruc.dk<= /a>>{=3D}ccl.net<http://ccl.net> [owner-che= mistry+spanget=3D=3Druc.dk&= lt;http://ruc.dk>{=3D}ccl.net<http://ccl.net>] p&#229; vegne af micaela matta micaela.matta2 .. unibo.it<http://unibo.= it> [owner-chemistry{=3D}ccl.net<http://ccl.ne= t>]
Sendt: 10. december 2013 17:05
Til: Jens Spanget-Larsen
Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high

Sent to CCL by: "micaela =A0matta" [micaela.matta2 .. unibo.it<http://unibo.= it>]
Dear CCL suscribers,

I am running TD-DFT calculations on an organic molecule at level CAM-BLYP/6= -
311G*. The first excited state has the correct energy compared to experimen= tal
results, but I obtained an unphysical f=3D2.7206!! How can I make sense of = this
result?
Thanks

Micaelahttp://www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/c= hemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt<http://www.= ccl.net/cgi-bin/ccl/send_ccl_messagehttp:/www.ccl.net/chemistry/sub_unsub.s= htmlhttp:/www.ccl.net/spammers.txt>


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<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">Dear Micaela,<o:p></o:p></span></= p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">According to &#8220;IUPAC Glossary of terms used i= n photochemistry, 3rd Edition, 2005&#8221;, the oscillator strength f i= s defined as:<o:p></o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span style=3D"font-size:10.= 0pt;font-family:&quot;Courier New&quot;;color:#1F497D">f = =3D (8*pi^2*m*c*nu)/(3*e^2*h) G * M^2
<o:p></o:p></span></p>
<p class=3D"MsoNormal"><span style=3D"font-size:10.= 0pt;font-family:&quot;Courier New&quot;;color:#1F497D"><= o:p>&nbsp;</o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">where m is the mass of the electron, c is the velocity= of light, nu is the wavenumber, e is the elementary charge, and h is the P= lanck constant. G is the
=A0degeneracy of the final state, and M is the transition moment vector. Fo= rmally, there is no upper limit to nu and the length of M, and there is thu= s no reason why the magnitude of f should not increase unity (however, acco= rding to the Thomas-Reiche-Kuhn sum
=A0rule, the sum of the oscillator strengths from one sub-state to all othe= r states is equal to the total number of electrons N).<o:p></o:p&g= t;</span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">Yors, Jens &gt;--&lt;<o:p></o:p>&l= t;/span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">P.S. Experimentally, f is determined by integration ov= er the entire absorption band-width of the molar decadic absorption coeffic= ient eps(nu), f =3D INT[eps(nu)dnu].<o:p></o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D"><o:p>&nbsp;</o:p></span></p&g= t;
<p class=3D"MsoNormal"><span lang=3D"EN-US" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp;
</span><span lang=3D"EN-GB" style=3D"font-size:10.0= pt;font-family:&quot;Courier New&quot;;color:#1F497D">-----= -------------------------------------------------<o:p></o:p><= ;/span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; JENS SPANGET-LARSEN&nbsp;&nbsp;&= ;nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Office:&nbsp;&= amp;nbsp;&nbsp;&nbsp;&nbsp; &#43;45 4674 2710<o:p><= ;/o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; Dept. of Science (18.1)&nbsp;&nbsp;= &nbsp;&nbsp; Fax:&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;= &nbsp;&nbsp;&nbsp; &#43;45 4674 3011<o:p></o:p>= </span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; Roskilde University&nbsp;&nbsp;&= ;nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Mobile:&nbsp;&= amp;nbsp;&nbsp;&nbsp;&nbsp; &#43;45 2320 6246<o:p><= ;/o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp; P.O.Box 260&nbsp;&nbsp;&nbsp;&a= mp;nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nb= sp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; E-Mail:&nbsp;&= ;nbsp;&nbsp;&nbsp;
<a href=3D"mailto:span= get#,#ruc.dk">s= panget#,#ruc.dk</a>&l= t;o:p></o:p></span></p>
<p class=3D"MsoNormal"><span lang=3D"EN-GB" st= yle=3D"font-size:10.0pt;font-family:&quot;Courier New&quot;;co= lor:#1F497D">&nbsp;
</span><span style=3D"font-size:10.0pt;font-family:&quot;= Courier New&quot;;color:#1F497D">DK-4000 Roskilde, Denmark&= nbsp;&nbsp;
<a href=3D"http://www.ruc.dk/~spanget">http://www.ruc.dk/~spanget</a><o:p>&= lt;/o:p></span></p>
<p class=3D"MsoNormal"><span style=3D"font-size:10.= 0pt;font-family:&quot;Courier New&quot;;color:#1F497D">&= ;nbsp;
</span><span lang=3D"EN-GB" style=3D"font-size:10.0= pt;font-family:&quot;Courier New&quot;;color:#1F497D">-----= -------------------------------------------------<o:p></o:p><= ;/span></p>
<p class=3D"MsoNormal"><span style=3D"font-size:11.= 0pt;font-family:&quot;Calibri&quot;,&quot;sans-serif&quot;;= color:#1F497D"><o:p>&nbsp;</o:p></span></p= >
<p class=3D"MsoNormal"><b><span lang=3D"EN-US= " style=3D"font-size:10.0pt;font-family:&quot;Tahoma&quot= ;,&quot;sans-serif&quot;">From:</span></b><s= pan lang=3D"EN-US" style=3D"font-size:10.0pt;font-family:&am= p;quot;Tahoma&quot;,&quot;sans-serif&quot;"> owner-chem= istry&#43;spanget=3D=3Druc.dk#,#ccl.net [mailto:owner-chem= istry&#43;spanget=3D=3Druc.dk#,#ccl.net]
<b>On Behalf Of </b>Micaela Matta micaela.matta2&#43;/-unibo.it<br>
<b>Sent:</b> 11. december 2013 09:29<br>
<b>To:</b> Jens Spanget-Larsen<br>
<b>Subject:</b> CCL: SV: TDDFT (CAM-B3LYP) oscillator strength = too high<o:p></o:p></span></p>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
<div>
<div>
<div>
<div>
<p class=3D"MsoNormal">Dear Jens,<o:p></o:p><= ;/p>
</div>
<p class=3D"MsoNormal">I thught it to be unreasonable becau= se oscillator strength must be less or equal than one, and this had never h= appened to me before.
<o:p></o:p></p>
</div>
<p class=3D"MsoNormal">Thank you very much to all of you!&l= t;o:p></o:p></p>
</div>
<p class=3D"MsoNormal">Micaela<o:p></o:p></p= >
<div>
<p class=3D"MsoNormal" style=3D"margin-bottom:12.0pt"= ;><o:p>&nbsp;</o:p></p>
<div>
<p class=3D"MsoNormal">2013/12/11 Somananda Sanyal somanand= a.sanyal]|[<a href=3D"http://gmail.com">gmail.com</a> &lt;<a href=3D"mailto:owner-chemistry..ccl.net" target=3D"_blank">owner-chemistry..ccl.net</a>&gt;<o:p></o:p><= /p>
<div>
<p class=3D"MsoNormal">Dear&nbsp;Micaela,<o:p><= ;/o:p></p>
<div>
<p class=3D"MsoNormal">&nbsp; &nbsp; The oscillator= strength you are getting using CAM-B3LYp, or for that matter many other fu= nctionals that I too have checked with, such f&gt;1 results come.<o:= p></o:p></p>
</div>
<div>
<p class=3D"MsoNormal">As far as I know, it is because of t= he fact that the oscillator strengths are not normalized, so that is why th= ey come as greater than 1 value.<o:p></o:p></p>
</div>
<div>
<p class=3D"MsoNormal"><o:p>&nbsp;</o:p><= ;/p>
</div>
<div>
<p class=3D"MsoNormal">Thanks and regards,<o:p></o= :p></p>
</div>
<div>
<p class=3D"MsoNormal">Somanand Sanyal<o:p></o:p&g= t;</p>
</div>
</div>
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<p class=3D"MsoNormal"><br clear=3D"all"> <o:p></o:p></p>
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<p class=3D"MsoNormal"><span style=3D"color:silver&= quot;>*****************</span><o:p></o:p></p> </div>
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<p class=3D"MsoNormal"><span style=3D"font-family:&= amp;quot;Tahoma&quot;,&quot;sans-serif&quot;;color:#999999"= ;>Regards,</span><o:p></o:p></p>
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<div>
<p class=3D"MsoNormal"><span style=3D"font-family:&= amp;quot;Tahoma&quot;,&quot;sans-serif&quot;;color:#999999"= ;>Somananda Sanyal.<br>
Theoretical Sciences Unit,<br>
JNCASR, Bangalore.</span><o:p></o:p></p>
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<p class=3D"MsoNormal">On Wed, Dec 11, 2013 at 4:23 AM, Jen= s Spanget-Larsen spanget,&#43;,<a href=3D"http://ruc.dk" target=3D"_blank"&= gt;ruc.dk</a> &lt= ;<a href=3D"mailto:owner-chemistry],[ccl= .net" target=3D"_blank">owner-chemistry],[ccl.net</a>&gt; wrote:<o:p></o:p= ></p>
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<blockquote style=3D"border:none;border-left:solid #CCCCCC 1.0pt;pa= dding:0cm 0cm 0cm 6.0pt;margin-left:4.8pt;margin-right:0cm">
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Sent to CCL by: Jens Spanget-Larsen [spanget[]<a href=3D"http://ruc.dk" target=3D"_b= lank">ruc.dk</a&= gt;]<br>
<br>
Dear Micaela,<br>
why do you think that an oscillator strength f =3D 2.7 is unphysical? This = is certainly a large value, but it is not necessarily unreasonable. With TD= -PBE1PBE/6-31&#43;G*, we obtained f =3D 2.2 &nbsp;for the first opt= ically allowed electronic transition in the D2d conformation
=A0of diphenyldiacetylene, see Thulstrup et al., PCCP 13, 16168-16174 (2011= ).<br>
Jens &gt;--&lt;<br>
<br>
&nbsp; ------------------------------------------------------<br>=
&nbsp; JENS SPANGET-LARSEN &nbsp; &nbsp; &nbsp; &nbsp; = Office: &nbsp; &nbsp; &nbsp;<a href=3D"tel:%2B45%204674%202710" tar= get=3D"_blank">&#43;45 4674 2710</a><br>
&nbsp; Dept. of Science (18.1) &nbsp; &nbsp; Fax: &nbsp; &a= mp;nbsp; &nbsp; &nbsp; <a href=3D"tel:%2B45%204674%203011" target=3D&qu= ot;_blank">
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&nbsp; DK-4000 Roskilde, Denmark &nbsp; <a href=3D"http://www.ruc.dk/~spange= t" target=3D"_blank">
http://www.ruc.dk/= ~spanget</a><br>
&nbsp; ------------------------------------------------------<br>=
<br>
________________________________________<br>
Fra: owner-chemistry&#43;spanget=3D=3D<a href=3D"http://ruc.dk" target=3D"_blank= ">ruc.dk</a>{= =3D}<a href=3D"http://= ccl.net" target=3D"_blank">ccl.net</a> [owner-chemistry&#43;spanget=3D=3D<a href=3D"http://ruc.dk" target=3D"_blank&qu= ot;>ruc.dk</a>{=3D= }<a href=3D"http://ccl= .net" target=3D"_blank">ccl.net</a>]
=A0p&amp;#229; vegne af micaela matta micaela.matta2 .. <a href=3D&q= uot;http://unibo.it"= target=3D"_blank">
unibo.it</a> [owner= -chemistry{=3D}<a href=3D"http://ccl.net" target=3D"_blank">ccl.net</a>]<br>
Sendt: 10. december 2013 17:05<br>
Til: Jens Spanget-Larsen<br>
Emne: CCL: TDDFT (CAM-B3LYP) oscillator strength too high<br>
<br>
Sent to CCL by: &quot;micaela &nbsp;matta&quot; [micaela.matta2= .. <a href=3D"http:/= /unibo.it" target=3D"_blank">
unibo.it</a>]<br= >
Dear CCL suscribers,<br>
<br>
I am running TD-DFT calculations on an organic molecule at level CAM-BLYP/6= -<br>
311G*. The first excited state has the correct energy compared to experimen= tal<br>
results, but I obtained an unphysical f=3D2.7206!! How can I make sense of = this<br>
result?<br>
Thanks<br>
<br>
Micaelahttp://<a href=3D"http://www.ccl.net/cgi-bin/ccl/send_ccl_m= essagehttp:/www.ccl.net/chemistry/sub_unsub.shtmlhttp:/www.ccl.net/spammers= .txt" target=3D"_blank">www.ccl.net/cgi-bin/ccl/send_ccl_messageht= tp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt</a><br>
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--

Hao-Bo Guo

BCMB Department

University of Tennessee Knoxville

Plant Systems Biology Group

Oak Ridge National Laboratory

865-803-4432; guoh1!=3Drnl.gov




--
Hao-Bo Guo
<= div>BCMB Department
University of Tennessee Knoxville
Plant Systems Biology Group
Oak Ridge National Laboratory
865-803-4432; guoh1-,-ornl.gov



--
<= div>
Hao-Bo Guo
BCMB Department
= University of Tennessee Knoxville
Plant Systems Biology Group
Oak Ridge National Laboratory
865-803-4432; guoh1-,-ornl.gov
--001a11365370e7155704ed6cd651-- From owner-chemistry@ccl.net Fri Dec 13 19:39:00 2013 From: "Franco franco.egidi- -gmail.com" To: CCL Subject: CCL:G: FC analysis after a TDDFT calculation Message-Id: <-49448-131213192834-4899-71PbPOnRvbArXKVTXhle1w*server.ccl.net> X-Original-From: Franco Content-Type: multipart/alternative; boundary=047d7bd6adbc59e55204ed73a896 Date: Sat, 14 Dec 2013 01:28:28 +0100 MIME-Version: 1.0 Sent to CCL by: Franco [franco.egidi[#]gmail.com] --047d7bd6adbc59e55204ed73a896 Content-Type: text/plain; charset=ISO-8859-1 You can force Gaussian to compute the vibronic transitions by using Freq=(FC,ReadFCHT) and adding the keyword ForceFCCalc in the ReadFCHT-specific line at the bottom of the input file. Add to the same line the keywords MaxC1=N and MaxC2=M, with high M and N (I suggest 60 and 40 respectively) to get high vibrational states in the excited PES. Your value for the <0'|0"> integral is very low though, so a meaningful spectrum probably cannot be extracted. Best, Franco Scuola Normale Superiore, Pisa, Italy 2013/12/13 Pierre Archirel pierre.archirel]*[u-psud.fr < owner-chemistry###ccl.net> > > Sent to CCL by: "Pierre Archirel" [pierre.archirel^_^u-psud.fr] > Dear colleagues, > I could optimise the geometry of an excited state with TDDFT and > gaussian09. > Asking for the Franck-Condon analysis (with simply freq=fc), I get the > answer: > > ERROR: The Franck-Condon factor corresponding to the overlap integral > between both vibrational ground states is too small: > |<0'|0">|^2 < 0.47904E-13 > > I understand that the two geometries are very different, but how can I ask > for upper vibrational levels in the excited state, so as to reach the FC > zone? > > Many thanks in advance, > Pierre Archirel > LCP, universite Paris-Sud > France > > pierre.archirel:u-psud.fr> > > --047d7bd6adbc59e55204ed73a896 Content-Type: text/html; charset=ISO-8859-1 Content-Transfer-Encoding: quoted-printable
You can force Gaussian to compute the vibro= nic transitions by using Freq=3D(FC,ReadFCHT) and adding the keyword ForceF= CCalc in the ReadFCHT-specific line at the bottom of the input file. Add to= the same line the keywords MaxC1=3DN and MaxC2=3DM, with high M and N (I s= uggest 60 and 40 respectively) to get high vibrational states in the excite= d PES. Your value for the <0'|0"> integral is very low thoug= h, so a meaningful spectrum probably cannot be extracted.

Best,
Franco
Scuola Normale Superiore,
Pisa,= Italy


2013/12/13 Pierre Archirel pierre.archirel]*[u-psud.fr <owner-chemistry###ccl.net>

Sent to CCL by: "Pierre =A0Archirel" [pierre.archirel^_^u-psud.fr]
Dear colleagues,
I could optimise the geometry of an excited state with TDDFT and gaussian09= .
Asking for the Franck-Condon analysis (with simply freq=3Dfc), I get the an= swer:

ERROR: The Franck-Condon factor corresponding to the overlap integral
=A0 between both vibrational ground states is too small:
=A0 |<0'|0">|^2 < =A00.47904E-13

I understand that the two geometries are very different, but how can I ask = for upper vibrational levels in the excited state, so as to reach the FC zo= ne?

Many thanks in advance,
Pierre Archirel
LCP, universite Paris-Sud
France

pierre.archirel:u-psud.fr



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