From chemistry-request@ccl.net Fri Jan 7 13:32:43 2005 Received: from icarus.it.wsu.edu (icarus.it.wsu.edu [134.121.1.46]) by server.ccl.net (8.12.8/8.12.8) with ESMTP id j07IWgvw024479 for ; Fri, 7 Jan 2005 13:32:42 -0500 Received: from [134.121.44.19] (tyr0.chem.wsu.edu [134.121.44.19]) by icarus.it.wsu.edu (8.12.10/8.12.10) with ESMTP id j07IndTk210568; Fri, 7 Jan 2005 10:49:39 -0800 (PST) In-Reply-To: <~BA00d5a02d.0025d245.mml.874217634{at}correio.cetem.gov.br> References: <~BA00d5a02d.0025d245.mml.874217634{at}correio.cetem.gov.br> Mime-Version: 1.0 (Apple Message framework v619) Content-Type: text/plain; charset=ISO-8859-1; format=flowed Message-Id: Cc: "'chemistry'" From: Kirk Peterson Subject: Re: CCL:TZ2P basis set and Bromine Date: Fri, 7 Jan 2005 10:49:33 -0800 To: Ian Hovell X-Mailer: Apple Mail (2.619) X-Virus-Scanned: by amavisd-milter (http://amavis.org/) X-Spam-Status: No, hits=0.0 required=7.5 tests=none autolearn=no version=2.61 X-Spam-Checker-Version: SpamAssassin 2.61 (1.212.2.1-2003-12-09-exp) on servernd.ccl.net Content-Transfer-Encoding: 8bit X-MIME-Autoconverted: from quoted-printable to 8bit by server.ccl.net id j07IWhvw024483 Ian, of course the full range of correlation consistent basis sets are available for bromine, DZ - 5Z. If they are not already in Gaussian, you can fetch them from the PNNL/EMSL website: http://www.emsl.pnl.gov/forms/basisform.html regards, Kirk -------------------------------------------- Kirk A. Peterson Professor of Chemistry and Materials Science Washington State University Pullman, WA 99164-4630 Office: (509) 335-7867 Fax: (509) 335-8867 kipeters{at}wsu.edu http://tyr0.chem.wsu.edu/~kipeters/ ------------------------------------------------------------------------ On Jan 6, 2005, at 10:20 AM, Ian Hovell wrote: > Dear CCLers, > > I recently made inquiries about the TZ2P basis set for use in > Gaussian. I have managed to find and use, thanks to the group in > particularly Wolfgang Roth, data for several atoms. I would like to > know if anyone knows of a TZ2P (or quality equivalent) basis set for > Bromine > > > > TIA > > > > Ian Hovell - Ph.D. > > NUCLEO DE MODELAGEM MOLECULAR-NMM > > Centro de Tecnologia Mineral - CETEM > > Ministerio da Cijncia e da Tecnologia- MCT > > Avenida Ipj, No 900 - Cidade Universitaria > > Ilha do Fundco Rio de Janeiro RJ Brasil > > CEP 21941-590 > > tel 00 55 (xx) 3865 7344 ou 3865 - 7216 > > Fax 00 55 (xx) 22602837 ou 2290-4286 > > e-mail hovell{at}cetem.gov.br > > From chemistry-request@ccl.net Fri Jan 7 00:47:07 2005 Received: from web51304.mail.yahoo.com (web51304.mail.yahoo.com [206.190.38.170]) by server.ccl.net (8.12.8/8.12.8) with SMTP id j075l57d007415 for ; Fri, 7 Jan 2005 00:47:05 -0500 Received: (qmail 35496 invoked by uid 60001); 7 Jan 2005 06:04:10 -0000 Comment: DomainKeys? See http://antispam.yahoo.com/domainkeys DomainKey-Signature: a=rsa-sha1; q=dns; c=nofws; s=s1024; d=yahoo.com; b=wP+t0PD/NvEkeOe5TybiQoVWMgdmHVFR5GiFl+BpMsaPqpjtAf8SNjR/JoZlub+nDNgtwn+Bvkmw7kU2SAGJRPD5rnnAzAK1Y3Lw/1iWJBx6WoqTogfiIHt7UQFpfdStrvX0ug7XRWcjAeHkWDAFqgMkFtOFUD+vZUz2ob3o4uo= ; Message-ID: <20050107060410.35494.qmail/at/web51304.mail.yahoo.com> Received: from [24.152.168.117] by web51304.mail.yahoo.com via HTTP; Thu, 06 Jan 2005 22:04:10 PST Date: Thu, 6 Jan 2005 22:04:10 -0800 (PST) From: Sengen Sun Subject: CCL: Re: CCL:orbitals and reality To: chemistry/at/ccl.net In-Reply-To: <41D855B8.1040305/at/trentu.ca> MIME-Version: 1.0 Content-Type: text/plain; charset=us-ascii X-Spam-Status: No, hits=-0.5 required=7.5 tests=SMILEY autolearn=no version=2.61 X-Spam-Checker-Version: SpamAssassin 2.61 (1.212.2.1-2003-12-09-exp) on servernd.ccl.net I wish to post my answers to Prof. Lewars' questions in this list. Please correct me if I am wrong anywhere. Photoelectron spectra should be accurately described by Schrodinger or Dirac equation if the accurate solutions (WF0, WF1, WF2, ... WFn,...) corresponding to the energy levels (E0, E1, E2, ..., En,...) could be obtained. And the maximum wave length should be accurately described by E1-E0. This would require that accurate WF0 and WF1 be multi-electron WFs. That is, each accurate solution must be a multi-electron WF. It is a common mistake to think that single molecular orbitals are rough solutions of S-equation. Instead, they are just mathematical constructs to make up each approximated solution, and are solely human made-staff for our convenience. 1) "why do the Woodward-Hoffmann rules work?" This is simply because our mathematics works. Our mathematics has been developed in such a way that the computational results reflect the physical reality or we fail. For example, a node separating two domains of electron cloud is reflected in our math by a phase transition. From negative to positive, we cannot miss zero, - a node. This is simply a mathematical technic. Matter waves are statistic waves, solely decided by positive density distribution. The phases have no physical meaning or no physical effect, but useful for mathematical operation. In atoms and molecules, one of the must-processes for fruitful computations is to perform overlap integrations. These integrals directly contributes in numerical quantities to the bond orders (or density distribution). Again, the phases can play the mathematical rule in adjusting the magnitude of integrals so that the physical reality is correctly reflected in the math. It is not surprising that there are some patterns based on the phases. It is just how mathematics works. It is coincident in some sense due to our choice of LCAO. Once a mathematical strategy is chosen, there must be consequent patterns in the mathematical scheme to correspond to the physical reality. The W-H rules are actually a qualitive correlation relationship derived from the mathematical operations, or an equivalence to mathematical index. They are very valuable to use but they have very limited explaining power. This relationship should be explained instead of explaining. The only explanation has to be based on the mathematical procedure or numerical quantities. We should limit what we can say about orbitals in the physical reality or we cause conceptual confusion. Of course, our human is not blind in choosing the mathematical constructs (to make up an approximate solution of the S-equation). It is based on plenty of earlier emperical knowledge and the earlier theoretical foundation that we have had the smart choice of the constructs. The constructs have the sole purpose of solving the S-equation despite of their ROUGH meaning in the physical reality. The HOMO is corresponding to the outer shell of the electron cloud. It is just again coincidental due to our mathematical technique. The critical thing here is that the physical relevence of HOMO is very ROUGH, and cannot be interpretted accurately. WFs have no physical meaning and cannot function physically. Therefore, There is no way to oberve or test them by physical experiements. Although electron density is the physcial reality, you still cannot measure a full orbital picture by electron density in a multielectron system. This is because there is no clear physical boundaries between single orbitals and electron density cannot function physically according to orbitals. The only thing we can do is to play mathematical tricks based on the picture of a ghost in our minds! 2) "why do photoelectron spectra correspond to the energy level picture?" Isn't this again a coincidence? :-) 3) "why do ionization energies equal (appoximately)the negative of HOMO energies?" Isn't this a coincidence too? I wouldn't think so if the word "appoximately" could be replaced by "accurately" :-)! These coincidences are too incredible to believe even for myself. I don't enforce my perception of the coincidences if any one does not agree. But what I can say more safely (as Prof. Richard Bader always likes to say something safe) is that no body has ever interpretted the meaning of orbital phases in the physical reality but in mathematics. Therefore, they surely don't know what they really "imaged"! Sorry for the lengthy polemics. Sengen --- errol lewars wrote: > 2004 Jan 2 > > Without taking sides in the recurring > reality-of-orbitals debate, I > would be interested to hear how some would respond > to the questions: > if orbitals have no physical reality, then > 1) why do the Woodward-Hoffmann rules work? > 2) why do photoelectron spectra correspond to the > energy level picture > provided by MO calculations? > 3) why do ionization energies equal (appoximately) > the negative of HOMO > energies? > > EL > ==== > __________________________________ Do you Yahoo!? Yahoo! Mail - Helps protect you from nasty viruses. http://promotions.yahoo.com/new_mail