From chemistry-request@server.ccl.net Thu Feb 15 19:24:50 2001 Received: from hotmail.com (f226.law10.hotmail.com [64.4.15.226]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1G0Oow07582 for ; Thu, 15 Feb 2001 19:24:50 -0500 Received: from mail pickup service by hotmail.com with Microsoft SMTPSVC; Thu, 15 Feb 2001 16:22:52 -0800 Received: from 128.97.139.222 by lw10fd.law10.hotmail.msn.com with HTTP; Fri, 16 Feb 2001 00:22:52 GMT X-Originating-IP: [128.97.139.222] From: "hu eric" To: chemistry@ccl.net Subject: WWW ccl.net Date: Thu, 15 Feb 2001 16:22:52 -0800 Mime-Version: 1.0 Content-Type: text/plain; charset=gb2312; format=flowed Message-ID: X-OriginalArrivalTime: 16 Feb 2001 00:22:52.0382 (UTC) FILETIME=[999F1FE0:01C097AE] Hi, CCLers Is there a WWW server that we can use for the ccl mails like the one Amber has? Thanks! Eric _________________________________________________________________________ Get Your Private, Free E-mail from MSN Hotmail at http://www.hotmail.com. From chemistry-request@server.ccl.net Thu Feb 15 23:59:28 2001 Received: from web12709.mail.yahoo.com (web12709.mail.yahoo.com [216.136.174.56]) by server.ccl.net (8.11.0/8.11.0) with SMTP id f1G4xRw08654 for ; Thu, 15 Feb 2001 23:59:27 -0500 Message-ID: <20010216045929.6217.qmail@web12709.mail.yahoo.com> Received: from [65.6.48.45] by web12709.mail.yahoo.com; Thu, 15 Feb 2001 20:59:29 PST Date: Thu, 15 Feb 2001 20:59:29 -0800 (PST) From: water Miller Subject: Analytical function for H-bond To: chemistry@ccl.net Cc: nano_fs@yahoo.com MIME-Version: 1.0 Content-Type: text/plain; charset=us-ascii Dear listers, I am wondering if anyone has the experience with deriving analytical functions for H-bond, classical or quantum, small or big system? As far as I know, the most used function may be the Morse function, and sometimes with angle dependence. If it's the case, how to get the Morse parameters? Simply do ab initio calculations for some points, fit it, run some kind of MD/MC calculations to compare with experimental quantities, or is there any better way? Any suggestion or reference will be highly appreciated! Water __________________________________________________ Do You Yahoo!? Get personalized email addresses from Yahoo! Mail - only $35 a year! http://personal.mail.yahoo.com/ From chemistry-request@server.ccl.net Fri Feb 16 00:52:50 2001 Received: from m2w037 (M2W037.mail2web.com [168.144.108.37]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1G5qow08922 for ; Fri, 16 Feb 2001 00:52:50 -0500 Received: from m2w037 [168.144.108.37] by m2w037 with ESMTP (SMTPD32-6.00) id A0347BEC00EE; Fri, 16 Feb 2001 00:52:52 -0500 X-Originating-IP: 161.142.100.85 X-URL: http://www.mail2web.com/ Subject: q.amber Sender: "nepenthes@vplaces.net" From: "nepenthes@vplaces.net" Date: Fri, 16 Feb 2001 00:52:52 -0500 To: "chemistry@ccl.net." Reply-To: rowyna@vplaces.net X-Priority: 3 X-MSMail-Priority: Normal MIME-Version: 1.0 Content-Type: text/plain; charset="iso-8859-1" X-Mailer: JMail 3.7.0 by Dimac (www.dimac.net) Message-Id: <200102160052485.SM00652@m2w037> Content-Transfer-Encoding: 8bit X-MIME-Autoconverted: from Quoted-Printable to 8bit by server.ccl.net id f1G5qow08923 Hello, I downloaded the q.amber script to assign partial charges but it gives me "/usr/bin/awk: arg list too long" message. I don't actually know how i can modify the file to run cos i read from the Autodock FAQ that you should modify the script. Hope somebody can help me with this. Thank you. Rowyn ISB University of Malaya T: +6(03)-7967 6745 -------------------------------------------------------------------- Mail2Web - Check your email from the web at http://www.mail2web.com/ . From chemistry-request@server.ccl.net Fri Feb 16 00:53:05 2001 Received: from m2w034 (M2W034.mail2web.com [168.144.108.34]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1G5r5w08933 for ; Fri, 16 Feb 2001 00:53:05 -0500 Received: from m2w034 [168.144.108.34] by m2w034 with ESMTP (SMTPD32-6.00) id A0422C5F00A6; Fri, 16 Feb 2001 00:53:06 -0500 X-Originating-IP: 161.142.100.85 X-URL: http://www.mail2web.com/ Subject: q.amber Sender: "nepenthes@vplaces.net" From: "nepenthes@vplaces.net" Date: Fri, 16 Feb 2001 00:53:06 -0500 To: "chemistry@ccl.net." Reply-To: rowyna@vplaces.net X-Priority: 3 X-MSMail-Priority: Normal MIME-Version: 1.0 Content-Type: text/plain; charset="iso-8859-1" X-Mailer: JMail 3.7.0 by Dimac (www.dimac.net) Message-Id: <200102160053113.SM01996@m2w034> Content-Transfer-Encoding: 8bit X-MIME-Autoconverted: from Quoted-Printable to 8bit by server.ccl.net id f1G5r5w08934 Hello, I downloaded the q.amber script to assign partial charges but it gives me "/usr/bin/awk: arg list too long" message. I don't actually know how i can modify the file to run cos i read from the Autodock FAQ that you should modify the script. Hope somebody can help me with this. Thank you. Rowyn ISB University of Malaya T: +6(03)-7967 6745 -------------------------------------------------------------------- Mail2Web - Check your email from the web at http://www.mail2web.com/ . From chemistry-request@server.ccl.net Fri Feb 16 05:37:10 2001 Received: from mail.wesleyan.edu (smtp.wesleyan.edu [129.133.1.61]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GAbAw09954 for ; Fri, 16 Feb 2001 05:37:10 -0500 Received: from yliu (yliu.stu.wesleyan.edu [129.133.164.85]) by mail.wesleyan.edu (8.9.3/8.9.1) with SMTP id FAA03325 for ; Fri, 16 Feb 2001 05:37:11 -0500 (EST) From: "Yongxing Liu" To: "CCL" Subject: Soft Sphere Simulation Code Date: Fri, 16 Feb 2001 05:42:54 -0500 Message-ID: MIME-Version: 1.0 Content-Type: text/plain; charset="iso-8859-1" Content-Transfer-Encoding: 7bit X-Priority: 3 (Normal) X-MSMail-Priority: Normal X-Mailer: Microsoft Outlook IMO, Build 9.0.2416 (9.0.2910.0) Importance: Normal X-MimeOLE: Produced By Microsoft MimeOLE V5.00.2919.6700 Dear sir, Has anyone used the soft sphere code (Appendix L) from the book <> by J. M. HAILE? Could anyone please point to me the address to download the lastest code? Thank you very much for your help! Sincerely Yongxing Liu From chemistry-request@server.ccl.net Fri Feb 16 07:22:26 2001 Received: from prserv.net ([32.97.166.34]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GCMQw11213 for ; Fri, 16 Feb 2001 07:22:26 -0500 Received: from attglobal.net (slip-32-101-131-196.in.us.prserv.net[32.101.131.196]) by prserv.net (out4) with SMTP id <2001021612221120405rq4p3e>; Fri, 16 Feb 2001 12:22:12 +0000 Message-ID: <3A8CD837.86EE9C8E@attglobal.net> Date: Fri, 16 Feb 2001 07:35:19 +0000 From: jmmckel@attglobal.net Reply-To: jmmckel@attglobal.net X-Mailer: Mozilla 4.51 [en]C-CCK-MCD (WinNT; I) X-Accept-Language: en MIME-Version: 1.0 To: chemistry@ccl.net Subject: Replacing PIII mobo's with AMD mobo's for comp chem Content-Type: text/plain; charset=us-ascii Content-Transfer-Encoding: 7bit Jesus Orduna recently asked about running G98 on AMD based machines. I have a related question: What are some experiences on replacing PIII/ motherboard with AMD/motherboard under under NT on existing systems? What software had to be reloaded? Were there major complications? I'll post a summary. John McKelvey From chemistry-request@server.ccl.net Fri Feb 16 04:00:15 2001 Received: from stan2.ch.pwr.wroc.pl (IDENT:postfix@stan2.ch.pwr.wroc.pl [156.17.3.203]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1G90Dw09646 for ; Fri, 16 Feb 2001 04:00:13 -0500 Received: by stan2.ch.pwr.wroc.pl (Postfix, from userid 500) id 8C7FEA4151; Fri, 16 Feb 2001 10:00:53 +0100 (CET) Received: from localhost (localhost [127.0.0.1]) by stan2.ch.pwr.wroc.pl (Postfix) with ESMTP id 82665A414C for ; Fri, 16 Feb 2001 10:00:53 +0100 (CET) Date: Fri, 16 Feb 2001 10:00:53 +0100 (CET) From: Stanislaw Kucharski To: chemistry@ccl.net Subject: refractive index Message-ID: MIME-Version: 1.0 Content-Type: TEXT/PLAIN; charset=US-ASCII Hi Netters, I am looking for a program to evaluate the refractive index of organic compounds. Any information will be welcome. With regards, -- Dr. Stanislaw Kucharski Wroclaw Technical University, Wroclaw, Poland Tel. +48 71 3202862; Fax: +48 71 3203678 E-Mail: stanley@stan2.ch.pwr.wroc.pl; kucharski@itots.ch.pwr.wroc.pl From chemistry-request@server.ccl.net Fri Feb 16 07:57:59 2001 Received: from mserv.itpa.lt (mserv.itpa.lt [193.219.53.20]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GCv4w11305 for ; Fri, 16 Feb 2001 07:57:47 -0500 Received: from localhost (tamulis@localhost) by mserv.itpa.lt (8.11.1/8.11.0) with ESMTP id f1GCteQ49861; Fri, 16 Feb 2001 14:55:45 +0200 (EET) (envelope-from tamulis@itpa.lt) Date: Fri, 16 Feb 2001 14:55:40 +0200 (EET) From: Arvydas Tamulis To: "Cust. Service Doug" cc: , , Jelena Tamuliene Subject: Re: CCL:Paramagnetically shifted 1H NMR spectra In-Reply-To: Message-ID: MIME-Version: 1.0 Content-Type: TEXT/PLAIN; charset=US-ASCII Dear Douglas Fox, I am not expert in relativistic effects but I shall try to explane these contributions refering on systematic description given in book R. McWeeny, B.T. Sutcliffe "Methods of Molecular Quantum Mechanics" Academic Press, London, 1969 while in Response Theory relativistic effects are calculating in new modern way. I expect that more will say authors of DALTON and DIRAC packages. fi1 The exact four component wavefunction FI={fi2} fi3 fi4 naturaly involves all relativistic effects but the for the obtaining NMR, etc. needs to convert this function to MO that takes many computing resources. That was done in DIRAC (see references J. Chem. Phys., 113:3996, 2000; J. Chem. Phys., 100:2118, 1994). In DALTON is using non-relativistic wavefunctions, and NMR shieldings for open-shell species are obtained using Response Theory with perturbation operators corresponding to Fermi Contact and others: electron nucleous- spin interactions terms and electron spin - magnetic field interaction (see J. Chem. Phys. 100:8179, 1994). Electron spin-spin interaction is not included in Dalton. With best wishes, Arvydas Tamulis ************************************************* On Thu, 15 Feb 2001, Cust. Service Doug wrote: > > > Dr. Tamulis, > > This is more the class of effect I was thinking about. It is > relativistic in that it involves adding spin terms to the hamiltonian > after the fact but I can believe it is a big enough effect to see > this kind of change. It is not relativistic in that no relativistic > terms are added explicitly in the hamiltonian. > > I have not read this paper but will check on it when I can get to a > library. I would appreciate other references your colleague might have. > We do have an exercise in Exploring Chemistry, (the blue book), which > shows the hyperfine interaction. > > > > > Dear Douglas Fox, > > > > Excuse me that in my previous letter I have wrote your name mistakenly. > > > > My knowledge about relativistic effects are coming from Lithuanian atom > > theory school initiated by Prof. A. Jucys and now in Lithuania it is > > difficult to get properly literature sources about relativistic effects > > in molecules but I will ask to do this my colleague Dr. J. Tamuliene who > > now is in UC-Davis for research visit. > > > > Enclosed please find interesting responce from Prof. David A. Case who > > advises how to calculate in G98 the hyperfine interaction between the > > proton and the electron spins using ESR Isotropic Fermi contact couplings. > > > > Please say your opinion concerning this possible partial evaluation of > > relativistic effects in G98 calculating NMR. > > > > With best regards, Arvydas Tamulis > > &&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& > > You need to compute the hyperfine interaction between the proton and > > the electron spins, then use this value to compute the paramagnetic shift > > you would see in NMR. The quantum program will typically think you are > > doing an > > "ESR" calculation, but the interaction is observable in both NMR and ESR. > > In Gaussian, look for output labelled "Isotropic Fermi contact couplings" > > in your output. > > YOu might check out Bertini, Turano & Vila, Chem. Rev. 93:2833 (1993). > > > > David A. Case | e-mail: case@scripps.edu > > Dept. of Molecular Biology, TPC15 | fax: +1-858-784-8896 > > The Scripps Research Institute | phone: +1-858-784-9768 > > 10550 N. Torrey Pines Rd. | home page: > > La Jolla CA 92037 USA | http://www.scripps.edu/case > > &&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& > > > > On Tue, 13 Feb 2001, Cust. Service Doug wrote: > > > > > > > > > > > > > > Dr. Tamulis, > > > > > > Thanks for the structure. Looking at this structure these two > > > protons look chemically very similar so if I understand your post > > > the spin coupling between these protons and the Cu or other centers > > > or is it really spin orbit corrections on the Cu which cause > > > such a change? > > > > > > G98 certainly does not have these but it is not clear which effect > > > you mean nor how relativistic effects would cause it. Spin-spin > > > coupling between the nuclei perhaps but I don't see the electron > > > spin-spin or spin-orbit contributions. Is there a source article which > > > describes these effects? > > > > > > > > > > > > > > Dear Dauoglas Fox and other Netters who responded me during last days > > > > concerning calculations of paramagnetically shifted 1H NMR spectra > > > > possessing up to 135 ppm values. > > > > > > > > During last days I clearified that for large (100 ppm) paramagnetic > > > > 1H shifts are responsible not good basis sets (only few ppm) and not > > > > electron correlations (only tens ppm) but including relativistic effects: > > > > 'electron spin-orbit', 'electron spin-spin', and 'electron spin - proton > > > > spin', etc. couplings. I do not know what relativism it is included in DALTON > > > > and DIRAC packages (maybe here can respond experts from these teams) but > > > > for my opinion if it is included 'electron spin - proton spin' coupling > > > > that should give these 100 ppm paramagnetic shifts in 1H NMR spectra. > > > > > > > > Maybe in other programs people are doing such a inclusions of > > > > 'electron spin - proton spin couplings'? > > > > I would be appreciate if somebody will allow me to perform trial calculations > > > > of biliverdin CuOEB molecule 1H NMR spectrum using DALTON, DIRAC or other > > > > program with implemented as much as possible relativistic effects. > > > > > > > > Thanking your in advance for further discussions and advises. > > > > > > > > Yours sincerely, Arvydas Tamulis > > > > Enclosed please find X-Ray geometry of CuOEB molecule in Angstroms: > > > > Cu1 0. 0. 0. > > > > O2 0.2239 -2.96653 -1.55039 > > > > N3 1.38133 -1.33544 -0.35323 > > > > N4 1.38119 1.34207 0.36885 > > > > C5 1.22628 -2.58553 -0.97483 > > > > C6 2.51385 -3.33756 -0.86868 > > > > C7 3.37827 -2.55016 -0.22896 > > > > C8 2.67395 -1.28282 0.09472 > > > > C9 3.26426 -0.17877 0.65202 > > > > C10 2.68854 1.08761 0.70813 > > > > C11 3.38244 2.34651 0.96318 > > > > C12 2.50269 3.34699 0.72477 > > > > C13 1.25013 2.71593 0.35196 > > > > C14 0.0751 3.37078 0. > > > > C15 2.68652 -4.68205 -1.49633 > > > > C16 3.05674 -4.56912 -2.96369 > > > > C17 4.84657 -2.77602 0.04178 > > > > C18 5.72923 -2.08939 -1.00856 > > > > C19 4.85471 2.43112 1.27447 > > > > C20 5.69449 2.34802 0.0041 > > > > C21 2.72592 4.83225 0.72854 > > > > C22 2.87181 5.41601 -0.67222 > > > > H23 4.13917 -0.29105 1.00274 > > > > H24 0.09707 4.35684 0. > > > > H25 1.8737 -5.18468 -1.40342 > > > > H26 3.37402 -5.20107 -1.07412 > > > > H27 3.13618 -5.45897 -3.37019 > > > > H28 2.36288 -4.06322 -3.3895 > > > > H29 3.87718 -4.07992 -3.05734 > > > > H30 5.00432 -3.74715 0.00503 > > > > H31 5.07799 -2.46117 0.91361 > > > > H32 6.64112 -2.28581 -0.82449 > > > > H33 5.51113 -2.4159 -1.88189 > > > > H34 5.58593 -1.11668 -0.96462 > > > > H35 5.10459 1.68705 1.84642 > > > > H36 5.03303 3.27735 1.73233 > > > > H37 6.61722 2.41078 0.21711 > > > > H38 5.52484 1.4978 -0.44582 > > > > H39 5.45344 3.10135 -0.56135 > > > > H40 3.50226 5.01567 1.24612 > > > > H41 1.98737 5.25961 1.1645 > > > > H42 3.01354 6.38803 -0.58859 > > > > H43 3.62122 5.00544 -1.10604 > > > > H44 2.09038 5.25163 -1.1876 > > > > N45 -1.43943 -1.27259 0.35323 > > > > N46 -1.32005 1.40226 -0.36885 > > > > C47 -1.12793 2.76892 -0.35196 > > > > C48 -1.34022 -2.52835 0.97483 > > > > C49 -2.72843 -1.16245 -0.09472 > > > > C50 -2.63743 1.20627 -0.70813 > > > > C51 -2.35113 3.45514 -0.72477 > > > > O52 -0.3558 -2.95361 1.55039 > > > > C54 -2.66 -3.22228 0.86868 > > > > C55 -3.4885 -2.39716 0.22896 > > > > C56 -3.26899 -0.0332 -0.65201 > > > > C57 -3.27458 2.49484 -0.96318 > > > > C58 -2.50799 4.94886 -0.72854 > > > > C59 -2.89238 -4.55775 1.49633 > > > > C60 -4.9654 -2.5574 -0.04178 > > > > H61 -4.14802 -0.1064 -1.00274 > > > > C62 -4.74161 2.64493 -1.27447 > > > > C63 -2.62775 5.53854 0.67222 > > > > H64 -3.2754 5.16668 -1.24612 > > > > H65 -1.75115 5.34291 -1.1645 > > > > C66 -3.2572 -4.42844 2.96368 > > > > H67 -2.10276 -5.09608 1.40342 > > > > H68 -3.60232 -5.04563 1.07412 > > > > C69 -5.8166 -1.83214 1.00856 > > > > H70 -5.16625 -3.52054 -0.00503 > > > > H71 -5.18257 -2.23255 -0.91362 > > > > C72 -5.58426 2.59932 -0.0041 > > > > H73 -5.02439 1.91273 -1.84642 > > > > H74 -4.88207 3.49828 -1.73233 > > > > H75 -2.72604 6.51592 0.58859 > > > > H76 -3.3947 5.16177 1.10604 > > > > H77 -1.85441 5.33953 1.1876 > > > > H78 -3.37619 -5.31387 3.37019 > > > > H79 -2.5415 -3.95395 3.3895 > > > > H80 -4.05504 -3.90319 3.05734 > > > > H81 -6.73633 -1.98774 0.82449 > > > > H82 -5.61326 -2.16804 1.88189 > > > > H83 -5.63012 -0.86678 0.96462 > > > > H84 -6.50328 2.70312 -0.21711 > > > > H85 -5.45265 1.74239 0.44582 > > > > H86 -5.3099 3.34117 0.56135 > > > > *********************************************************** > > > > > > > > > > > > > On Mon, 12 Feb 2001, Cust. Service Doug wrote: > > > > > > > > > > > > > > Dr. Tamulis, > > > > > > > > > > I don't have ready access to this journal at my office. Can > > > > > you send the structure you used? Have you verified that the > > > > > environment around these protons is reasonably described by this > > > > > input structure? > > > > > > > > > > Generally the shifts in proton NMR calculations are good only to > > > > > about 10% which makes them less appropriate for structural studies > > > > > but the wide range you report from the experiment should be reproduced > > > > > at least qualitatively. > > > > > > > > > > > > > > > > > Dear Netters, > > > > > > > > > > > > We did not succeeded to calculate paramagnetically shifted 1H NMR spectrum > > > > > > of biliverdin molecule CuOEB using Gaussian 98 (see experimental data in > > > > > > J. Am. Chem.Soc., vol. 115, p. 12206 (1993)). > > > > > > > > > > > > We have optimized geometry of TeMeSilane molecule and obtained from NMR > > > > > > calculation the Isotropic Shielding values for H atoms (in ppm): > > > > > > > > > > > > H Isotropic = 31.9027 Anisotropy = 9.6413 > > > > > > XX= 29.4642 YX= 0.2951 ZX= -0.7329 > > > > > > XY= 0.4642 YY= 32.9871 ZY= -5.1492 > > > > > > XZ= -0.8947 YZ= -5.1015 ZZ= 33.2567 > > > > > > Eigenvalues: 27.9348 29.4430 38.3302 > > > > > > > > > > > > We have used Density Functional Theory B3PW91/6-311G** > > > > > > > > > > > > We have taken geometry of CuOEB from X-Ray experiment. > > > > > > Our B3PW91\6-311G** calculated CuOEB NMR Hm shielding values (ppm): > > > > > > 23 H Isotropic = 28.4781 Anisotropy = 10.0683 > > > > > > XX= 24.0637 YX= -1.2135 ZX= -.8179 > > > > > > XY= -.0906 YY= 35.1141 ZY= -2.2717 > > > > > > XZ= 9.0739 YZ= 1.6948 ZZ= 26.2566 > > > > > > Eigenvalues: 20.8808 29.3633 35.1904 > > > > > > > > > > > > 60 H Isotropic = 27.5216 Anisotropy = 12.3793 > > > > > > XX= 22.4061 YX= 2.7621 ZX= -1.0495 > > > > > > XY= -.3733 YY= 35.4454 ZY= 2.7019 > > > > > > XZ= 10.0293 YZ= -6.4196 ZZ= 24.7134 > > > > > > Eigenvalues: 18.6646 28.1258 35.7745 > > > > > > > > > > > > and shielding Hm' value: > > > > > > 24 H Isotropic = 25.8868 Anisotropy = 16.3237 > > > > > > XX= 36.5750 YX= -.6396 ZX= 4.7813 > > > > > > XY= -.0379 YY= 23.9614 ZY= .1694 > > > > > > XZ= -.9100 YZ= 2.3766 ZZ= 17.1241 > > > > > > Eigenvalues: 16.7005 24.1907 36.7693 > > > > > > > > > > > > It means that our calculated chemical shifts for Hm and Hm' are equal to > > > > > > few ppm while CuOEB experimental NMR chemical shift values for Hm and Hm' in > > > > > > J. Am. Chem.Soc., vol 115, p. 12206 are equal approximately to 135 ppm and > > > > > > -100 ppm. > > > > > > > > > > > > Why so badly we have calculated paramagnetically shifted 1H NMR spectrum > > > > > > for CuOEB molecule? > > > > > > Maybe GAUSSIAN is not able to calculate paramagnetically shifted 1H NMR > > > > > > spectra? > > > > > > Which program is suitable for calculations of paramagnetically shifted 1H > > > > > > NMR spectra? > > > > > > > > > > > > Thanking your in advance. > > > > > > With best regards, Arvydas Tamulis & Jelena Tamuliene > > > > > > ******************************************************* > > > > > > Arvydas Tamulis > > > > > > > > > > > > Doctor of Natural Sciences, senior research fellow > > > > > > > > > > > > Institute of Theoretical Physics and Astronomy, > > > > > > Theoretical Molecular Electronics Research Group, > > > > > > A. Gostauto 12, Vilnius 2600, Lithuania > > > > > > e-mail: TAMULIS@ITPA.lt; WEBsite: http://www.itpa.lt/~tamulis/ > > > > > > fax: +(370-2)-225361 or +(370-2)-224694 > > > > > > Phone: +(370-2)-620861 > > > > > > Home address: Didlaukio 27-40, Vilnius 2057, Lithuania > > > > > > Phone: +(370-2)-778743 > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > -= This is automatically added to each message by mailing script =- > > > > > > CHEMISTRY@ccl.net -- To Everybody | CHEMISTRY-REQUEST@ccl.net -- To Admins > > > > > > MAILSERV@ccl.net -- HELP CHEMISTRY or HELP SEARCH > > > > > > CHEMISTRY-SEARCH@ccl.net -- archive search | Gopher: gopher.ccl.net 70 > > > > > > Ftp: ftp.ccl.net | WWW: http://www.ccl.net/chemistry/ | Jan: jkl@ccl.net > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > > -- > > > > > > > > > > Douglas J. Fox > > > > > Technical Support > > > > > Gaussian, Inc. > > > > > help@gaussian.com > > > > > > > > > > > > > > > > > > > > > > > -- > > > > > > Douglas J. Fox > > > Technical Support > > > Gaussian, Inc. > > > help@gaussian.com > > > > > > > > > > > -- > > Douglas J. Fox > Technical Support > Gaussian, Inc. > help@gaussian.com > > From chemistry-request@server.ccl.net Fri Feb 16 09:49:29 2001 Received: from ergo.ibaf.cs.cnr.it ([194.119.197.4]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GEnSw11723 for ; Fri, 16 Feb 2001 09:49:29 -0500 Received: from unicz.it (ergo.ibaf.cs.cnr.it [194.119.197.4]) by ergo.ibaf.cs.cnr.it (8.11.0/8.11.0/SuSE Linux 8.11.0-0.4) with ESMTP id f1GEoOk17549 for ; Fri, 16 Feb 2001 15:50:24 +0100 X-Authentication-Warning: ergo.ibaf.cs.cnr.it: Host ergo.ibaf.cs.cnr.it [194.119.197.4] claimed to be unicz.it Sender: workshop@cs.cnr.it Message-ID: <3A8D3E30.E0870CA6@unicz.it> Date: Fri, 16 Feb 2001 15:50:24 +0100 From: 1st workshop in Magna Graecia Organization: =?iso-8859-1?Q?Universit=E0?= degli Studi di Catanzaro "Magna Graecia" X-Mailer: Mozilla 4.76 [en] (X11; U; Linux 2.2.16 i686) X-Accept-Language: en MIME-Version: 1.0 To: chemistry@ccl.net Subject: Second Circular of the 1st Medicinal Chemistry Workshop in Magna Graecia Content-Type: text/plain; charset=iso-8859-1 Content-Transfer-Encoding: 8bit X-MIME-Autoconverted: from quoted-printable to 8bit by server.ccl.net id f1GEnTw11724 Dear CCL Colleague, the Organizing Committee is pleased to inform you about the second circular of the "First Magna Gręcia Medicinal Chemistry Workshop on New Perspectives in Drug Research" 10-13 June 2001, Copanello (CZ) Italy. The following renowned speakers have already confirmed their partecipation to the Workshop: Prof. S. Hanessian, Prof. P.Goodford, Prof. G. Richards, Prof. M. Karelson, Prof. R. S. Coleman and Prof. J.Briggs. The main topics of the Workshop are organized in specific sessions names as follows: New Methodologies in Drug Design Molecular Modeling and Drug Research Drug Development of NOS inhibitors Receptor-targeted Drug Design Anticancer Agents Antiviral Agents A Poster Session and two Free communications Sessions will be organized during the meeting as well as social activities. For further information please visit our website http://www.unicz.it/ricerca/convegni/ or e-mail to mailto:workshop@unicz.it If you are interested to submit an abstract or to subscribe to the Workshop, please remember the following important dates: Abstract submission Thursday, February 28, 2001 Standard Registration Saturday, March 31, 2001 Accommodation Saturday March 31, 2001 Looking forward for your application. Best regards The Organizing Commitee "Insieme per la Ricerca" From chemistry-request@server.ccl.net Fri Feb 16 11:39:35 2001 Received: from mailserv.wright.edu (mailserv.wright.edu [130.108.128.60]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GGdZw12337 for ; Fri, 16 Feb 2001 11:39:35 -0500 Received: from CONVERSION-DAEMON.mailserv.wright.edu by mailserv.wright.edu (PMDF V6.0-24 #45557) id <0G8U00A01ZM06K@mailserv.wright.edu> for CHEMISTRY@ccl.net; Fri, 16 Feb 2001 11:39:36 -0500 (EST) Received: from unconfigured (o137142.wright.edu [130.108.137.142]) by mailserv.wright.edu (PMDF V6.0-24 #45557) with SMTP id <0G8U0096QZLZ8H@mailserv.wright.edu>; Fri, 16 Feb 2001 11:39:36 -0500 (EST) Date: Fri, 16 Feb 2001 11:39:31 -0500 From: Kevin Gross Subject: Summary: DFT and Koopmans' theorem To: CCL Cc: chrirena@techunix.technion.ac.il Reply-to: Kevin Gross Message-id: <005f01c09837$09b2a620$8e896c82@wright.edu> MIME-version: 1.0 X-MIMEOLE: Produced By Microsoft MimeOLE V5.50.4522.1200 X-Mailer: Microsoft Outlook Express 5.50.4522.1200 Content-type: text/plain; charset=Windows-1252 Content-transfer-encoding: 8BIT X-Priority: 3 X-MSMail-priority: Normal Thank you for all the insightful responses regarding DFT and Koopmans' theorem. My question was simple: >Does Koopmans' theorem still hold for MO energies obtained from DFT >calculations? I'm curious because I've found that HOMO & LUMO energies >obtained from HF calculations are much better regression descriptors >than are the energies taken from identical B3LYP calcs. Any comments or >references regarding this topic will be summarized. To summarize most of the responses, Koopmans' theorem does not hold for DFT. Of course, DFT is not an MO method, so it doesn't make sense to even talk about HOMOs or LUMOs (nonetheless, to avoid HOKSO/LUSKO terminology, it is understood that in DFT, a HOMO energy refers to the eigenvalue of the highest occupied Kohn-Sham orbital). Apparently, though, some interpretation of the Kohn-Sham orbital energies is possible. Being that B3LYP is a hybrid of HF and DFT, it seems as though Koopmans' theorem does not apply to this specific case. The individual responses are below. Thanks, Kevin Gross Wright State University Dayton, OH 45435 ----------------------------------------------------------------------- kevin - perhaps you should read "what do the kohn-sham orbitals and eigenvalues mean?" in JACS, 1999, _121_, 3414-3420 by stowasser and hoffman. regards, steve t ----------------------------------------------------------------------- Kevin - Koopmans' Theorem generally performs poorly when combined with DFT in my experience. The reason HF tends to work well is because HF ignores correlation effects and Koopmans' Theorem ignores electronic relaxation of the newly created cation. We get 'lucky' in that the two tend to balance out. With DFT, the correlation is not neglected, so there is nothing to balance out the poor approximation that Koopmans' Theorem makes. Dave -- Dr. David J. Giesen Eastman Kodak Company david.giesen@kodak.com 2/83/RL MC 02216 (ph) 1-716-58(8-0480) Rochester, NY 14650 (fax)1-716-588-1839 ----------------------------------------------------------------------- No, they don't. The fact that the B3LYP energies are not good descriptors in a regression analysis is interesting, and I would offer one word of caution before you consider this a firm conclusion: Don't simply regress on 'HOMO energies'. Instead, regress on 'MO energies' where you choose MO's of similar shape (this cautionary statement applies to both HF and DFT energies). DFT frequently orders MOs differently than HF, and you might find that HOMO shapes are not correlated with each other (in which case one does not expect a systematic variation in HOMO energy). -Alan ==== Alan Shusterman Department of Chemistry 3203 SE Woodstock Blvd Reed College Portland, OR 97202 503-771-1112, ext. 7699 ----------------------------------------------------------------------- First B3LYP is not truly a KS-DFT method. It mixes KS-DFT and HF; because of that I think that neither Janak theorem nor Koopmans' theorem apply in B3LYP, but I'm not sure, I haven't checked. The question of Koopmans' theorem and KS-DFT is often asked, I recall it's been discussed many times on CCL so it may be in the archives. In my opinion, Koopmans' theorem is not so important anyway: it relates a theoretical construct (HF orbital energies) to another theoretical construct (the energy difference between the HF ground state and a hypothetical state in which HF orbitals do not relax relative to GS). There IS something similar to a Koopmans' theorem in DFT, it's Janak's theorem. It states that: (dE/dn_i) = e_i (e_i = i'th orbital energy) [Janak, Phys. Rev. B 18 (1978) 7165] the derivative of the total energy w.r.t. to occupation number of orbital "i" is exactly the orbital-energy (Kohn-Sham eigenvalue) "i". This is true not only for the (unknown) exact exchange-correlation potential but for all commonly used approximate XC potentials. From this formula one can in principle get ionization potentials by integrating e_i over dn_i, between 1 and 0 (between 0 and 1 for an electron affinity). An approximation to this integral is to take the value of the integrand at the midpoint, e_i(n_i=1/2), and multiply by the range of integration which is just (+/-)one (add/remove one electron), which gives Slater's transition state approximation for IPs: IP(Slater's TS) = - e_i(n_i=1/2) [ Slater, Adv. Quantum Chem. 6 (1972) 1 ; Slater, "The SCF field for Molecules and Solids: Quantum Theory of Molecules and Solids", vol. 4, New York (McGraw Hill, 1974) ] Williams et al. refined Slater's formula, they got a better approximation to the integral for n_i from 1 to 0, see [ Williams et al.. J. Chem. Phys. 63 (1975) 628 ] In a sense Janak's theorem is better than Koopmans' theorem because it relates a theoretical construct to a real thing (if we integrate e_i for n_i from 1 to 0, or from 0 to 1). IF ONE HAD THE EXACT EXCHANGE-CORRELATION POTENTIAL, one would get the EXACT lowest ionization potential by integrating Janak's formula; Slater's formula is an approximation to that. I append an answer given by Kiet Nguyen to a related question below, it contains useful references. Cheers, Rene. -------------------------------------------------------------------- | Rene Fournier | Bureau/Office 458 CCB | | Chemistry, York University | (416) 736 2100 Ext. 30687 | | 4700 Keele Street, North York | FAX: (416) 736-5936 | | Ontario, CANADA M3J 1P3 | e-mail: renef@yorku.ca | -------------------------------------------------------------------- #10 Kiet Nguyen, Kiet.Nguyen@wpafb.af.mil Although there is considerable controversy in the literature concerning the meaning of Kohn-Sham orbitals, I think they are far from "meaningless". This topic has been carefully analyzed and reviewed.[1-5] Parr and Yang stated that "... one should expect no simple physical meaning for the Kohn-Sham orbital energies."[3] However, using the Janak theorem which "provides a meaning for the eigenvalues of the Kohn-Sham equation", they have connected the HOMO and LUMO energies to the ionization potential and electron affinity, respectively.[3] [1] E. J. Baerends and O. V. Gritsenko, J. Phys. Chem. A 101 (1997) 5383. [2] R. G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules (University Press, Oxford, 1989). [3] J. P. Perdew, in: Density Functional Methods in Physics, edited by R. M. Dreizler and J. da Providencia New York, 1985), p. 265 [4] E. J. Baerends and O. V. Gritsenko, J. Phys. Chem. A 101 (1997) 5383. [5] R. Stowasser and R. Hoffman, J. Am. Chem. Soc. 121 (1999), 3414. Kiet A. Nguyen AFRL/MLPJ Laser Hardened Materials Branch Wright-Patterson AFB, OH 45433 Phone (937) 255-6671, Ext 3178 FAX (937) 255-1128 ========== ----------------------------------------------------------------------- We touch this question briefly and refer to the relevant literature in GI Csonka, BG Johnson Theor Chem Acc (1998) 99: 158-165 paper: "Perdew, Parr et al. [1982 Phys. Rev. Lett.] showed that the exact KS potential and its E(HOMO) change discontinuously as the electron number N passes through an integer M. E(HOMO) is -I for N just below M, -(I+A)/2 for N=M, and -A for N just above M, where -A is the negative of the electron affinity." and "LSDA and GGA, which miss the derivative discontinuity, effectively average over it, providing an estimate of -(I+A)/2 for the E(HOMO)." So Koopmans theorem does not hold for B3LYP. For further details see the book of RG Parr and W Yang [1989] and Perdew's work I hope this helps, with best regards -- Gabor I. Csonka Budapest University of Technology FAX: (361) 463.36.42 Inorganic Chemistry Dept. Ch. Bldg csonka@web.inc.bme.hu H-1111, Bp. Szent Gellert ter 4 http://web.inc.bme.hu/~csonka/csg.html http://www.ch.bme.hu/inc/csg.html ----------------------------------------------------------------------- Dear Kevin: I guess that with the true functional and within the Kohn-Sham scheme the energy of the HOMO corresponds to the first ionization potential. I don’t remember where is published the proff, If I find it i will send you the reference. Armando Navarro Facultade de quimica Departamento de quimica organica Santiago de Compostela Spain ----------------------------------------------------------------------- No, Koopmans' theorem is derived with explicit reference to HF theory. Regarding Kohn-Sham orbitals computed with modern DFT, the following references should be of interst to you: P. Politzer, F. Abu-Awwad: "A comparative analysis of Hartree-Fock and Kohn.Sham orbital energies", Theor. Chem. Acc. 99, 83-87 (1998) R. Stowasser, R. Hoffmann: "What Do the Kohn-Sham Orbitals and Eigenvalues Mean?", J. Am. Chem. Soc. 121, 3414-3420 (1999) Briefly: It is found that Kohn-Sham MO energies differ significantly > from HF MO energies, but they tend to be linearly related. Jens >--< =-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-= JENS SPANGET-LARSEN Phone: +45 4674 2000 (RUC) Department of Chemistry +45 4674 2710 (direct) Roskilde University (RUC) Fax: +45 4674 3011 P.O.Box 260 E-Mail: JSL@virgil.ruc.dk DK-4000 Roskilde, Denmark http://virgil.ruc.dk/~jsl/ =-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-= ----------------------------------------------------------------------- Hi, this is an interesting problem .. and I've been able to find a very nice article to describe just that (Koopman's for DFT in terms of occupied and virtual orbitals in comparison with HF) .. look at: R Stowasser, R Hoffmann, JACS, 1999, 121, 3414 .. hope this helps !! bye serge ----------------------------------------------------------------------- Dear kevin, the eigenvalues connected to the Kohn-Sham (KS) orbitals do not have a strict physical meaning. In KS theory there is no equivalent of Koopmans' theorem, which could relate orbital energies to ionization energies. However, as a direct consequence of the long-range behaviour of the charge density, the eigenvalue of the HOMO of the KS orbitals equals the negative of the exact ionization energy. This, however, is only true if the essentially exact exchange-correlation potential is used . See A. Savin, C.J. Umriger, X. Gonze, Chem. Phys. Lett. 288 (1998) 391 for details. Best regards Klaus ----------------------------------------------------------------------- From chemistry-request@server.ccl.net Fri Feb 16 13:32:05 2001 Received: from sungod.ccs.yorku.ca (sungod.ccs.yorku.ca [130.63.236.104]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GIW4w12848 for ; Fri, 16 Feb 2001 13:32:04 -0500 Received: from sunrise.ccs.yorku.ca (sunrise.ccs.yorku.ca [130.63.236.87]) by sungod.ccs.yorku.ca (8.9.3/8.9.3) with ESMTP id NAA21817; Fri, 16 Feb 2001 13:32:04 -0500 (EST) Received: from localhost (serge@localhost) by sunrise.ccs.yorku.ca (8.9.3/8.9.3) with ESMTP id NAA22725; Fri, 16 Feb 2001 13:32:00 -0500 (EST) X-Authentication-Warning: sunrise.ccs.yorku.ca: serge owned process doing -bs Date: Fri, 16 Feb 2001 13:31:57 -0500 (EST) From: "S.I.Gorelsky" X-X-Sender: To: Kevin Gross cc: Subject: Re: CCL:Summary: DFT and Koopmans' theorem In-Reply-To: <005f01c09837$09b2a620$8e896c82@wright.edu> Message-ID: MIME-Version: 1.0 Content-Type: TEXT/PLAIN; charset=US-ASCII > To summarize most of the responses, Koopmans' theorem does not hold for > DFT. Of course, DFT is not an MO method, so it doesn't make sense to > even talk about HOMOs or LUMOs ... I disagree strongly with such a statement, and I think I am not alone. It is still make sense to talk about HOMOs and LUMOs. All depends how and where you can talk about them. Please check this Roald Hoffmann's paper R Stowasser, R Hoffmann, JACS, 1999, 121, 3414 Based on my own experince, I should say that the "molecular orbitals" obtained from DFT are quite similar to the molecular orbitals from standard MO-LCAO methods, and one can extract a lot of useful information about molecular systems from analysis of their MOs even if the density functional methods are used. Sergey Gorelsky York University, CANADA From chemistry-request@server.ccl.net Fri Feb 16 13:43:05 2001 Received: from mailserv.wright.edu (mailserv.wright.edu [130.108.128.60]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GIh5w12919 for ; Fri, 16 Feb 2001 13:43:05 -0500 Received: from CONVERSION-DAEMON.mailserv.wright.edu by mailserv.wright.edu (PMDF V6.0-24 #45557) id <0G8V001015BVN9@mailserv.wright.edu> for CHEMISTRY@ccl.net; Fri, 16 Feb 2001 13:43:07 -0500 (EST) Received: from unconfigured (o137142.wright.edu [130.108.137.142]) by mailserv.wright.edu (PMDF V6.0-24 #45557) with SMTP id <0G8V00MCF5BVSA@mailserv.wright.edu>; Fri, 16 Feb 2001 13:43:07 -0500 (EST) Date: Fri, 16 Feb 2001 13:42:32 -0500 From: Kevin Gross Subject: Re: CCL:Summary: DFT and Koopmans' theorem To: "S.I.Gorelsky" Cc: CCL Reply-to: Kevin Gross Message-id: <001901c09848$38d19360$8e896c82@wright.edu> MIME-version: 1.0 X-MIMEOLE: Produced By Microsoft MimeOLE V5.50.4522.1200 X-Mailer: Microsoft Outlook Express 5.50.4522.1200 Content-type: text/plain; charset=iso-8859-1 Content-transfer-encoding: 7bit X-Priority: 3 X-MSMail-priority: Normal References: Perhaps I was unclear. I am talking about HOMO/LUMO as being meaningless from a semantic point of view. DFT uses Kohn-Sham orbitals to arrive at the electron density and so the highest occupied orbital is perhaps better termed HOKSO for Highest Occupied Kohn-Sham Orbital. I thought the parenthetical comment you left out may have cleared this up. In context, I said: >Of course, DFT is not an MO method, so it doesn't make sense to >even talk about HOMOs or LUMOs (nonetheless, to avoid HOKSO/LUKSO >terminology, it is understood that in DFT, a HOMO energy refers to the >eigenvalue of the highest occupied Kohn-Sham orbital). Sorry for the confusion. Kevin Gross ----- Original Message ----- From: "S.I.Gorelsky" To: "Kevin Gross" Cc: Sent: Friday, February 16, 2001 1:31 PM Subject: Re: CCL:Summary: DFT and Koopmans' theorem : : > To summarize most of the responses, Koopmans' theorem does not hold for : > DFT. Of course, DFT is not an MO method, so it doesn't make sense to : > even talk about HOMOs or LUMOs : ... : : I disagree strongly with such a statement, and I think I am not : alone. It is still make sense to talk about HOMOs and LUMOs. All : depends how and where you can talk about them. Please check this Roald : Hoffmann's paper : : R Stowasser, R Hoffmann, JACS, 1999, 121, 3414 : : Based on my own experince, I should say that the "molecular orbitals" : obtained from DFT are quite similar to the molecular orbitals from : standard MO-LCAO methods, and one can extract a lot of useful information : about molecular systems from analysis of their MOs even if the density : functional methods are used. : : Sergey Gorelsky : : York University, CANADA : : From chemistry-request@server.ccl.net Fri Feb 16 13:55:50 2001 Received: from magnum.cooper.edu (magnum.cooper.edu [199.98.16.4]) by server.ccl.net (8.11.0/8.11.0) with SMTP id f1GItew12981 for ; Fri, 16 Feb 2001 13:55:45 -0500 Received: from robin.cooper.edu by magnum.cooper.edu with SMTP id AA11927 (5.65c/IDA-1.4.4 for ); Fri, 16 Feb 2001 13:51:25 -0500 Received: from localhost by robin.cooper.edu (SMI-8.6/SMI-SVR4) id NAA06127; Fri, 16 Feb 2001 13:51:12 -0500 Date: Fri, 16 Feb 2001 13:51:12 -0500 (EST) From: "Robert Q. Topper" To: CHEMISTRY@ccl.net Cc: ECCC7 Scientific Organizing Committee -- Dave Ferguson , Francis Muguet , "J.M.L. Gershom Martin" , Mark Tuckerman , Robert Topper , Yi-Ping Liu , ECCC7 Web Organizing Commitee -- HOPKINS BOB , Dominic Coluccio , Heather Hauck , LENT CHRISTOPHER P , MISZPUTEN RENEE , Sung-Hyun Son , TOPPER ROBERT Subject: ECCC7 Abstracts Due in One Week In-Reply-To: Message-Id: Mime-Version: 1.0 Content-Type: TEXT/PLAIN; charset=US-ASCII Just a reminder to everyone that abstracts for ECCC7 are due at the latest by Friday, February 23 - one week from today. Abstracts may be submitted online at http://eccc7.cooper.edu Review of abstracts will take place almost immediately thereafter. We hope to notify everyone of their submission's status by March 2. Registration for ECCC7 is scheduled to begin on March 5, and the conference will begin on April 2. I want to strongly encourage participants in the Spring ACS meeting, as well as the RECOMB meeting, to participate in ECCC7 as well. This is a perfect forum for you to share an electronic version of your poster or presentation online! Best regards, Robert ***************************************************************************** ELECTRONIC COMPUTATIONAL CHEMISTRY CONFERENCE APRIL 2001 http://eccc7.cooper.edu ***************************************************************************** Robert Q. Topper, Ph.D. email: topper@cooper.edu Associate Professor of Chemistry phone: (212) 353-4378 School of Engineering fax: (212) 353-4341 The Cooper Union for the Advancement of Science and Art subway: take the 6 to Astor Place 51 Astor Place or the N/R to 8th street New York, NY 10003 and you're there! ***************************************************************************** http://www.cooper.edu/engineering/chemechem/ ***************************************************************************** From chemistry-request@server.ccl.net Fri Feb 16 16:08:24 2001 Received: from mr.usu.edu (mr.usu.edu [129.123.1.3]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1GL8Nw13475 for ; Fri, 16 Feb 2001 16:08:23 -0500 Received: from tapaskar (tapaskar.chem.usu.edu [129.123.3.37]) by mr.usu.edu (Postfix) with SMTP id 504B91D3D6; Fri, 16 Feb 2001 14:08:22 -0700 (MST) Message-ID: <007001c0985c$756c0300$25037b81@tapaskar> From: "Tapas Kar" To: "S.I.Gorelsky" , "Kevin Gross" Cc: References: Subject: Re: CCL:Summary: DFT and Koopmans' theorem Date: Fri, 16 Feb 2001 14:07:24 -0700 X-Priority: 3 X-MSMail-Priority: Normal X-Mailer: Microsoft Outlook Express 5.50.4133.2400 X-MIMEOLE: Produced By Microsoft MimeOLE V5.50.4133.2400 I agree with Sergey. We compared local quantities such as bond indices, atomic charges, valences etc obtained from HF and KS. Please see J. Phys. Chem A 200, 104, 9953-9963. No appreciable difference is noticed except slightly enhanced covalency by KS orbitals. ------------------------------------------------ "We owe a lot to the Indians, who taught us how to count, without which no worthwhile scientific discovery could have been made." - Albert Einstein - ------------------------------------------------ Tapas Kar, Ph. D Department of Chemistry & Biochemistry Utah State University Logan, UT 84322-0300 Tel: 435-797-7230 Fax: 435-797-3390 Email: tapaskar@cc.usu.edu tapas@risky3.chem.usu.edu ----- Original Message ----- From: "S.I.Gorelsky" To: "Kevin Gross" Cc: Sent: Friday, February 16, 2001 11:31 AM Subject: CCL:Summary: DFT and Koopmans' theorem > > > To summarize most of the responses, Koopmans' theorem does not hold for > > DFT. Of course, DFT is not an MO method, so it doesn't make sense to > > even talk about HOMOs or LUMOs > >... > > I disagree strongly with such a statement, and I think I am not > alone. It is still make sense to talk about HOMOs and LUMOs. All > depends how and where you can talk about them. Please check this Roald > Hoffmann's paper > > R Stowasser, R Hoffmann, JACS, 1999, 121, 3414 > > Based on my own experince, I should say that the "molecular orbitals" > obtained from DFT are quite similar to the molecular orbitals from > standard MO-LCAO methods, and one can extract a lot of useful information > about molecular systems from analysis of their MOs even if the density > functional methods are used. > > Sergey Gorelsky > > York University, CANADA > > > > -= This is automatically added to each message by mailing script =- > CHEMISTRY@ccl.net -- To Everybody | CHEMISTRY-REQUEST@ccl.net -- To Admins > MAILSERV@ccl.net -- HELP CHEMISTRY or HELP SEARCH > CHEMISTRY-SEARCH@ccl.net -- archive search | Gopher: gopher.ccl.net 70 > Ftp: ftp.ccl.net | WWW: http://www.ccl.net/chemistry/ | Jan: jkl@ccl.net > > > > >