From DSMITH %-% at %-% uoft02.utoledo.edu Tue Dec 7 11:06:28 1993 Received: from uoft02.utoledo.edu for DSMITH (+ at +) uoft02.utoledo.edu by www.ccl.net (8.6.4/930601.1506) id KAA00248; Tue, 7 Dec 1993 10:36:06 -0500 Received: from UOFT02.UTOLEDO.EDU by UOFT02.UTOLEDO.EDU (PMDF V4.2-10 #3438) id <01H6718VQMAO004RR2 $#at#$ UOFT02.UTOLEDO.EDU>; Tue, 7 Dec 1993 10:35:54 EST Date: Tue, 07 Dec 1993 10:35:54 -0500 (EST) From: "DR. DOUGLAS A. SMITH, UNIVERSITY OF TOLEDO" Subject: Zinc Basis Sets - Summary (edited) To: chemistry { *at * } ccl.net Message-id: <01H6718VROVM004RR2.,at,.UOFT02.UTOLEDO.EDU> X-Envelope-to: chemistry -x- at -x- ccl.net X-VMS-To: CHEMISTRY MIME-version: 1.0 Content-transfer-encoding: 7BIT Appended is the summary of responses I received to my recent request for basis sets useful in the calculation of ZnR2 compounds. I have also included a general note from Tom Cundari from over a year ago regarding calculations on transition metals. Doug Douglas A. Smith Assistant Professor Department of Chemistry and member, Center for Drug Design and Development The University of Toledo Toledo, OH 43606-3390 voice 419-537-2116 fax 419-537-4033 email dsmith at.at uoft02.utoledo.edu =========================================================================== From: IN%"scheiner { *at * } biosym.com" 1-DEC-1993 20:22:25.73 To: IN%"dsmith <-at-> uoft02.utoledo.edu" CC: Subj: basis set for ZnR2 Doug, Take a look at the following publication: A. Schaefer, H. Horn, and R. Ahlrichs, "Fully Optimized Contracted Gaussian Basis Sets for Atoms Li to Kr", J. Chem. Phys. Vol. 97, pp. 2571-2577 (1992). No specific applications are reported, however, the basis sets for the first row transition metals are of valence double-zeta and full double-zeta quality, and should do reasonably well for the organo-zinc compounds of interest. - Andy ================================================================ Andrew C. Scheiner Phone: (619) 546-5346 Biosym Technologies, Inc. scheiner "-at-" biosym.com ================================================================ From: IN%"msrge %! at !% csv.warwick.ac.uk" "Mr C Wilson" 2-DEC-1993 06:08:00.56 To: IN%"DSMITH &$at$& uoft02.utoledo.edu" CC: Subj: RE: basis set for ZnR2? Either of the Los Alamos basis sets : LANL1MB LANL1DZ references for both basis sets are : P.J.Hay and W.R.Wadt J.Chem.Phys,82 pages 270-299 (1985) Craig From: IN%"jamorskc $#at#$ CHIMCN.UMontreal.CA" 2-DEC-1993 08:43:37.27 To: IN%"dsmith - at - uoft02.utoledo.edu" CC: Subj: RE: basis set for ZnR2? Hi Doug, we did some calculation on ZnCH3 using two different all electron basis set here they are: MIDI 4 (13s,7p,4d) -> [5s,3p,2d]: plus two p polarization orbitals (alpha=0.176, 0.055) ref: S.Huzinaga edited by Elsevier - Amsterdam- Oxford- New-York- Tokyo 1984 Watcher Basis set (14s,11p,5d) -> [6s,5p,2d] ref: A.J.H.Watchers, J.Chem.Phys. vol. 52, p1033 (1969). with contraction of: L.Gianolo,R.Pavani,E.Clementi, Societa Chimica Italiana p108 (1978) regards, Christine Jamorski From: IN%"young <-at-> slater.cem.msu.edu" 2-DEC-1993 09:01:06.06 To: IN%"dsmith[ AT ]uoft02.utoledo.edu" CC: Subj: Zn basis sets Hi, In response to your question about ZnR2 compounds. First of all, as with any approximation, you must ask yourself what exactly you want to determine and whether you want qualitative or quantitative answers and how accurate. However, as far as ab initio work, you will find that the most commonly used basis sets for that row of the transition series are Wachters basis J. H. Wachters, J. Chem. Phys. vol 53, no 3, 1 Feb (1970), p. 1033 which is a generalized contraction and Hay's segmented contraction set P. J. Hay, J. Chem. Phys., vol 66, no 10, 15 May (1977), p. 4377 These basis sets are often uncontracted further or have additional even tempered exponents added. For a look at some nice ab initio work, look at articles by Bauschlicker or Harrison. A few points of note on this type of calculation. Transition metals are fairly easy to deal with when they are in their preferred coordination. However, the low coordination compounds that are only stable in the gas phase can be tricky to deal with. They have many orbital energies and electronic states that are nearly degenerate. This leads to problems with convergence, converging to the correct state and contaminated wave functions. Convergence can be forced by the use of forced routines, such as the direct minimization in Gaussian. Converging to the desired state can be controlled by the construction of the initial guess (we often construct it by hand). If contaminated wave functions are a problem for the questions you are asking, you can work in a program such as COLUMBUS, where you have complete control over the symmetry constraints, usually at the expense of a terribly complex input. In short, you may find yourself in one of three situations. Your problem may work fine the first time. You may decide it's not worth the trouble. You may have a lot of work and fun gaining an in depth knowledge and mastery of ab initio techniques. Good luck. Dave Young young %-% at %-% slater.cem.msu.edu youngdc()at()msucem From: IN%"CUNDARIT%MEMSTVX1.BITNET()at()OHSTVMA.ACS.OHIO-STATE.EDU" 29-OCT-1992 23:17:48.42 To: IN%"chemistry ( ( at ) ) ccl.net" CC: Subj: More TM calcs. Concerning TM calcs, I'd like to follow up on Thersa Windus' comments on transition metal calcs. We've probably used GAMESS (Iowa State version) as extensively for transition metals as anyone else and from our point of view the big benefit to GAMESS is the built-in ECPs from Walt Stevens and co., the so-called SBKJs (Can. J. Chem. 1992, 70, 612). We have had quite good success in predicting geometries, rotational barriers, reaction barriers and the like using the SBKJs, which are formally triple-zeta for the "valence" nd, (n+1)s and (n+1)p. They also include the (n-1)s and (n-1)p outer core which the concensus seems to indicate are essential. To my knowledge, the SBKJ for the s- and p-block elements are built in Gaussian, but not for the d-block although they can be entered manually. Now that the SBKJs have been published I encourage anyone interested in getting into TM-containing systems to give them a whirl in their favorite program. Folks have, of course, have taken the basic Hay-Wadt scheme and augmented the basis sets and done some excellent TM work; the research of Morokuma, Hall and their collaborators come to my mind, but undoubtedly there are others. The work of Gernot Frenking is the first methodical analysis that I have seen of the various core size and basis set augmentation schemes for the Hay-Wadt. I highly recommend Gernot's article to anyone planning on getting into TM calcs. There are also the ECP schemes of Ross, Ermler, Pitzer, et al.; if my understanding is correct, this group has now extended their scheme to the entire Periodic Table! Doesn't CADPAC include Huzinaga's model potentials for the d-block? Preuss and company have published ECP schemes for the lanthanides, and we have extended the SBKJ scheme to the lanthanides. Thus, the ECP options in ab-initio calcs. are rapidly growing, definitely worth a look for anyone interested in the nether regions of the Periodic Table. Tom Cundari Assistant Professor Department of Chemistry Memphis State University Memphis, TN 38152 From: IN%"kauppm(-(at)-)CHIMCN.UMontreal.CA" 2-DEC-1993 10:14:00.50 To: IN%"dsmith.,at,.uoft02.utoledo.edu" CC: Subj: ZnR2 Dear Dr. Smith, somebody passed me your request for information on ZnR2 calculations. In fact, we had the same problem some years ago, as we were interested in some alkyl transfer reactions. So we tested several pseudopotential/ basis set combinations on M(CH3)2 and M(CH3) (M=Zn,Mg). This is published in J. Comp. Chem. 1990,11,1029-1037. The extensive applications we made can be found in J.Am.Chem.Soc. 1991,113,5606. Actually, these studies were part of my diplom thesis. I am presently spending some time in Canada, and my present address is given below. Please feel free to ask for more information. With best regards, Martin Kaupp ************************************************************ * Dr. Martin Kaupp * * Departement de chimie * * Universite de Montreal Fax (514) 343-2468 * * C.P. 6128, Succ. A Tel. (514) 343-6111-3991 * * Montreal, Quebec H3C 3J7 * * Canada * * email kauppm' at \`chims1.chimcn.umontreal.ca * ************************************************************ From: IN%"hommes \\at// organik.uni-erlangen.de" "Nico van Eikema Hommes" 3-DEC-1993 03:10:21.67 To: IN%"DSMITH.,at,.uoft02.utoledo.edu" CC: Subj: RE: basis set for ZnR2 Hello Doug! We have good experiences with the basis sets recently developed by the Ahlrichs group in Karlsruhe. See J.Chem.Phys. 97, 2571 (1992). The basis set files are available via anonymous ftp from tchibm3.chemie.uni-karlsruhe.de (129.13.108.8) We have the split-valence and the largest (TZ or DZ) basis sets converted to Gaussian-92 format. Email me if you would like a copy. Also, the newer pseudopotentials by Hay and Wadt as well as the Stuttgart pseudopotentials work fine. Gernot Frenking from Marburg recently published research using these in J.Comp.Chem. Second derivatives may not be available for these (Gaussian 92 does not have them, for instance), but they are very good e.g. for high-level single points. Greetings from Erlangen. Nico -- +=====================================+================================+ | Dr. N.J.R. van Eikema Hommes | hommes : at : organik.uni-erlangen.de | | Institut fuer Organische Chemie I | Tel. : 49/0 - 9131 - 85 - 4096 | | Henkestr. 42, D-91054 Erlangen, FRG | Fax : - 9132 | +=====================================+================================+ From: IN%"d3e129 #*at*# cagle.pnl.gov" 3-DEC-1993 10:47:49.91 To: IN%"DSMITH -8 at 8- uoft02.utoledo.edu" CC: Subj: basis set for ZnR2? Doug, I don't know the reference off the top of my head but David Funk and Grzegorz Chalasinski did some work with Zinc when Dave was a grad student at Utah. As I recall the open d-shell on the Zn atoms caused some strange sensitivities in the basis set. The results should have been published post 1985. This ain't much info but hopefully it will help some. Regards, Rick Kendall ============================================================================= === Ricky A. Kendall === === Mail Stop K1-90 === === Molecular Science Software Group === === Theory, Modeling, and Simulation Program === === Molecular Science Research Center === === Pacific Northwest Laboratory === === Richland, WA 99352 === === Phone: (509) 375-2602 === === Fax: (509) 375-6916 === =============================================================================