From owner-chemistry@ccl.net Fri Aug 21 01:39:01 2015 From: "Ruud Kenneth kenneth.ruud .. uit.no" To: CCL Subject: CCL: Excited state polarizability Message-Id: <-51606-150821013801-30652-+4ZjaptIjBvKQ6Z7i0CcvQ ~~ server.ccl.net> X-Original-From: Ruud Kenneth Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_E5A914B76A9B44F1A887EB3DA12273BAuitno_" Date: Fri, 21 Aug 2015 05:37:52 +0000 MIME-Version: 1.0 Sent to CCL by: Ruud Kenneth [kenneth.ruud!=!uit.no] --_000_E5A914B76A9B44F1A887EB3DA12273BAuitno_ Content-Type: text/plain; charset="Windows-1252" Content-Transfer-Encoding: quoted-printable I cannot answer for what is possible in g09, though I would assume it possi= ble to calculate the excited-state polarizability using at least finite-dif= ference methods. Excited-state polarizabilities (including their dispersion= ) can be calculated analytically in Dalton, however. Dalton is available fr= ee of charge, www.daltonprogram.org. Best regards, Kenneth Kenneth Ruud Prorector of Research, UiT - The Arctic University of Norway Telephone: +47 77623101 http://www.ctcc.no/people/senior-scientists/ruud/index.html On Aug 20, 2015, at 6:48 AM, Kaushik Hatua kaushikhatua#,#yahoo.in wrote: Is it possible to calculate excited state polarizability in g09 Sent from Nokia Lumia --_000_E5A914B76A9B44F1A887EB3DA12273BAuitno_ Content-Type: text/html; charset="Windows-1252" Content-ID: <5201AC446D02B141BC76AC0A797176F2###asp.uit.no> Content-Transfer-Encoding: quoted-printable I cannot answer for what is possible in g09, though I would assume it possi= ble to calculate the excited-state polarizability using at least finite-dif= ference methods. Excited-state polarizabilities (including their dispersion= ) can be calculated analytically in Dalton, however. Dalton is available free of charge, www.daltonprogram.org.


Best regards,

Kenneth

Kenneth Ruud
Prorector of Research, UiT - The Arctic University of Norway
Telephone: +47 77623101
htt= p://www.ctcc.no/people/senior-scientists/ruud/index.html

On Aug 20, 2015, at 6:48 AM, Kaushik Hatua kaushikhatua#,#yahoo.in wro= te:

Is it poss= ible to calculate excited state  polarizability in g09

Sent from Nokia Lumia

--_000_E5A914B76A9B44F1A887EB3DA12273BAuitno_-- From owner-chemistry@ccl.net Fri Aug 21 09:04:01 2015 From: "Kaushik Hatua kaushikhatua:_:yahoo.in" To: CCL Subject: CCL: Excited state polarizability Message-Id: <-51607-150821085011-2978-xGRtYbUBxE/IxSvH9bIO1A]~[server.ccl.net> X-Original-From: Kaushik Hatua Content-Type: multipart/alternative; boundary="_C6F02DDC-4C2B-48E9-99B9-CE827902DB20_" Date: Fri, 21 Aug 2015 18:19:54 +0530 MIME-Version: 1.0 Sent to CCL by: Kaushik Hatua [kaushikhatua],[yahoo.in] --_C6F02DDC-4C2B-48E9-99B9-CE827902DB20_ Content-Transfer-Encoding: quoted-printable Content-Type: text/plain; charset="utf-8" Thanks for your reply. I have seen it is under double residue of cubic resp= onse. I guess I could obtain excited state polarizability of vertical state= only and for adiabatic state I have to optimized the target state then go = for the same by simple response calculation.=20 Sent from Nokia Lumia=20 -----Original Message----- > From: "Ruud Kenneth kenneth.ruud .. uit.no" Sent: =E2=80=8E21-=E2=80=8E08-=E2=80=8E2015 01:01 PM To: "Hatua, Kaushik " Subject: CCL: Excited state polarizability I cannot answer for what is possible in g09, though I would assume it possi= ble to calculate the excited-state polarizability using at least finite-dif= ference methods. Excited-state polarizabilities (including their dispersion= ) can be calculated analytically in Dalton, however. Dalton is available fr= ee of charge, www.daltonprogram.org.=20 Best regards, Kenneth Kenneth Ruud Prorector of Research, UiT - The Arctic University of Norway Telephone: +47 77623101 http://www.ctcc.no/people/senior-scientists/ruud/index.html On Aug 20, 2015, at 6:48 AM, Kaushik Hatua kaushikhatua#,#yahoo.in wrote: Is it possible to calculate excited state polarizability in g09 Sent from Nokia Lumia = --_C6F02DDC-4C2B-48E9-99B9-CE827902DB20_ Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="utf-8" =0A= = =0A= =0A=
Thanks for your reply. I have seen it is under = double residue of cubic response. I guess I could obtain excited state pola= rizability of vertical state only and for adiabatic state I have to optimiz= ed the target state then go for the same by simple response calculation.
Sent from Nokia Lumia
From= : = Ruud Kenneth kenneth.ruud .. uit= .no
Sent: =E2=80=8E21-=E2=80=8E08-=E2=80=8E2015 01:01= PM
To: Hatua, K= aushik
Subject: CCL: Excited state polarizab= ility

=0A= I cannot answer for what is possible in g09, though I would assume it possi= ble to calculate the excited-state polarizability using at least finite-dif= ference methods. Excited-state polarizabilities (including their dispersion= ) can be calculated analytically=0A= in Dalton, however. Dalton is available free of charge, =0A= www.daltonprogram.org.=0A=

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Best regards,
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Kenneth
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Kenneth Ruud
=0A= Prorector of Research, UiT - The Arctic University of Norway
=0A= Telephone: +47 77623101
=0A= htt= p://www.ctcc.no/people/senior-scientists/ruud/index.html
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On Aug 20, 2015, at 6:48 AM, Kaushik Hatua kaushikhatua#,#yahoo.in wro= te:
=0A=
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Is it poss= ible to calculate excited state  polarizability in g09
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=0A= =0A= =0A= = --_C6F02DDC-4C2B-48E9-99B9-CE827902DB20_-- From owner-chemistry@ccl.net Fri Aug 21 11:34:00 2015 From: "Ruud Kenneth kenneth.ruud(!)uit.no" To: CCL Subject: CCL:G: Excited state polarizability Message-Id: <-51608-150821113009-30917-78Oaq1Brrno49z4xyhxwuA^_^server.ccl.net> X-Original-From: Ruud Kenneth Content-Language: en-US Content-Type: multipart/alternative; boundary="_000_D1FD10043023Ekennethruuduitno_" Date: Fri, 21 Aug 2015 15:29:41 +0000 MIME-Version: 1.0 Sent to CCL by: Ruud Kenneth [kenneth.ruud###uit.no] --_000_D1FD10043023Ekennethruuduitno_ Content-Type: text/plain; charset="us-ascii" Content-Transfer-Encoding: quoted-printable Yes, this would be the approach for calculating the excited-state polarizab= ility of the adiabatic state. Note that with Dalton, only LSDalton can curr= ently optimize the geometry of an excited state. However, this can als be d= one with other programs such as Turbomol and Gaussian (I believe). Let me perhaps also add that if the system is of a size that allows you to = do MCSCF calculations, you can of course explicitly optimize the excited st= ate and use linear response theory to calculate the polarizability of this = explicitly optimized excited state. Best regards, Kenneth > From: > on behalf of "Kaushik Hatua kaushikh= atua:_:yahoo.in" > Reply-To: CCL Subscribers > Date: Friday, August 21, 2015 2:49 PM To: Kenneth Ruud > Subject: CCL: Excited state polarizability Thanks for your reply. I have seen it is under double residue of cubic resp= onse. I guess I could obtain excited state polarizability of vertical state= only and for adiabatic state I have to optimized the target state then go = for the same by simple response calculation. Sent from Nokia Lumia ________________________________ --_000_D1FD10043023Ekennethruuduitno_ Content-Type: text/html; charset="us-ascii" Content-ID: <30960342DB6DED4A9D762596DA2CFFBD~!~asp.uit.no> Content-Transfer-Encoding: quoted-printable
Yes, this would be the approach for calculating the excited-state pola= rizability of the adiabatic state. Note that with Dalton, only LSDalton can= currently optimize the geometry of an excited state. However, this can als= be done with other programs such as Turbomol and Gaussian (I believe).

Let me perhaps also add that if the system is of a size that allows yo= u to do MCSCF calculations, you can of course explicitly optimize the excit= ed state and use linear response theory to calculate the polarizability of = this explicitly optimized excited state.


Best regards,

Kenneth

From: <owner-chemistry+kenneth.= ruud=3D=3Duit.no~!~ccl.net> on behalf of "Kaushik Hatua kaushikha= tua:_:yahoo.in" <owner-c= hemistry~!~ccl.net>
Reply-To: CCL Subscribers <chemistry~!~ccl.net>
Date: Friday, August 21, 2015 2:49 = PM
To: Kenneth Ruud <kenneth.ruud~!~uit.no>
Subject: CCL: Excited state polariz= ability

Thanks for= your reply. I have seen it is under double residue of cubic response. I gu= ess I could obtain excited state polarizability of vertical state only and = for adiabatic state I have to optimized the target state then go for the same by simple response calculation.

Sent from Nokia Lumia

--_000_D1FD10043023Ekennethruuduitno_-- From owner-chemistry@ccl.net Fri Aug 21 18:36:01 2015 From: "Lars Goerigk lars.goerigk[*]unimelb.edu.au" To: CCL Subject: CCL:G: UV-Visible spectrum Message-Id: <-51609-150821182541-26655-j3OzxHNopRRcfLrNx3yGWA_-_server.ccl.net> X-Original-From: Lars Goerigk Content-Language: en-AU Content-Transfer-Encoding: 8bit Content-Type: text/plain; charset="Windows-1252" Date: Fri, 21 Aug 2015 22:25:24 +0000 MIME-Version: 1.0 Sent to CCL by: Lars Goerigk [lars.goerigk()unimelb.edu.au] Hi, I assume you probably have an error of 1 eV or more for your TD-HF calculations? This is not a big surprise as HF does not include any electron correlation effects, neither does CIS, by the way, and its errors are of the same magnitude as for TD-HF. If you want to stick with wave function theory, you would need to use an electron-correlation method, such as SCS-CIS(D), CC2, CC3, CCSDR(3), etc. Someone else has already pointed out that benzene is reasonably small and highly symmetric, so with an efficient QM code you should be able to tackle this molecule with a wave function approach. That being said, of course TD-DFT would offer you a cost-effective alternative, but you have to be very careful with your choice of the functional. If you want to read more about this, I highly recommend to look up the various TD-DFT benchmark studies published by the Jacquemin or Grimme groups. For typical organic chromophores roughly these rules of thumb apply: 1) Do NOT rely on a GGA or meta-GGA functional (BP86, PBE, BLYP, TPSS etc.). Not only are the excitation energies wrong by about 0.5 eV, but these functionals suffer from self-intereaction error which produces artificial ghost states, i.e. low-lying states (of usually low intensity) that have no real counterpart. 2) The problem of ghost states can be partially solved by changing to a hybrid functional. However, even popular functionals such as B3LYP (20% Fock exchange) or PBE0 (25% Fock exchange) can still produce ghost states. The more Fock exchange you include the less ghost states you produce, but the more blue-shifted (overestimated) your energies become. For medium-sized organic chromophores it turns out that a value of around 40% of Fock-exchange is reasonable and absolute errors for organic dyes are on average around 0.2 eV. 3) If you want to be more accurate, you have to use a double-hybrid, such as B2PLYP or B2GPPLYP. Someone has already mentioned B2PLYPD. Two small comments on that. The “D” stands for the DFT-D dispersion correction and that will not have any influence on your excitation energies whatsoever, as it is an additive correction that does not directly influence your orbitals. The second comment is that a TD-B2PLYP calculation with Gaussian is not possible. Gaussian09 Rev A may claim to run such a calculation, however, the final result is not a TD-B2PLYP one. After I had pointed that out to the Gaussian developers, they made sure that in later revisions Gaussian aborts when B2PLYP is combined with the TD keyword. The only available code that allows for such calculations is Frank Neese’s ORCA, which is a freely available code and I recommend you look into this. 4) If you want to treat charge-transfer excitations, you will need a range-separated hybrid functional. 5) Use a triple-zeta basis set at least. 6) Never trust only one TD-DFT result. Run calculations with two functionals that differ in their amount of Fock exchange. In that way, you get a good idea on what states are ghost states and what are not. Now, these points were rather general, as for the benzene molecule: Grimme showed in two papers in 2003 that conventional functionals get the first two excited states in benzene and polycyclic aromatic hydrocarbons wrong. We also call these states La and Lb states. Later it was shown that range-separated hybrids improve the La excitation energies but they overestimate the Lb-type excitations. Double hybrids were the only functionals that provided a balanced description of La and Lb states: JCTC 2011, 7, 3272. Furthermore, benzene is a pretty standard example. I recommend a thorough literature research on it. I am certain that there are many papers out there that have already treated this molecule with accurate methods. I hope this helped. Cheers, Lars --- Dr. Lars Goerigk ARC DECRA Fellow School of Chemistry The University of Melbourne VIC 3010 Australia Research profile: http://www.chemistry.unimelb.edu.au/dr-lars-goerigk List of my publications: http://www.researcherid.com/rid/D-3717-2009 Follow me on Twitter: https://twitter.com ________________________________________ > From: owner-chemistry+lars.goerigk==unimelb.edu.au##ccl.net [owner-chemistry+lars.goerigk==unimelb.edu.au##ccl.net] on behalf of Kaci Tiziouzou kaci.tiziouzou/./gmail.com [owner-chemistry##ccl.net] Sent: Thursday, 20 August 2015 7:11 AM To: Lars Goerigk Subject: CCL:G: UV-Visible spectrum Hi all, Can anyone share with me the procedure that I can use to get a UV-VIS spectrum for Benzene. I am currently using the TD-SCF in gaussian 09 with a 6-31G basis set (Hartree Fock) and my value is way below the experimental. I must be doing something wrong!! Thanks in advance K.T