From cramer@maroon.tc.umn.edu Sat Oct 22 00:22:01 1994 Received: from maroon.tc.umn.edu for cramer@maroon.tc.umn.edu by www.ccl.net (8.6.9/930601.1506) id XAA05908; Fri, 21 Oct 1994 23:47:51 -0400 From: Received: by maroon.tc.umn.edu; Fri, 21 Oct 94 19:27:53 -0500 Message-Id: <2ea85c892be0002@maroon.tc.umn.edu> Subject: ANS: AMSOL performance To: bowlus@palres.dnet.sandoz.com (Steve Bowlus) Date: Fri, 21 Oct 1994 19:27:52 -0500 (CDT) Cc: chemistry@ccl.net, mf12101@uc.msc.edu (Don Truhlar) In-Reply-To: <199410212057.AA14087@tigger.jvnc.net> from "Steve Bowlus" at Oct 21, 94 04:47:07 pm X-Mailer: ELM [version 2.4 PL23] MIME-Version: 1.0 Content-Type: text/plain; charset=US-ASCII Content-Transfer-Encoding: 7bit Content-Length: 3779 Steve, > > I am running Amsol 4.5 on an Indigo2 (150Mhz), trying to do solvation > energies of compounds with ca. 15 heavy atoms. These systems optimize for > the gas phase in about 2 cpu minutes using the keyword "AM1". For the > solvation, I am using "AM1 SM2" and 4 cpu _hours_ later, things are still > chugging along. I have no experience with the solvation models, and would > like know what order of magnitude of cpu times I should be expecting. Also > , are there keyword combinations which will reduce this (I haven't tinkered > with e.g. PULAY, since the gas phase calculation went so quickly)? > I feel I can answer this question fairly authoritatively . . . The SMx solvation models as presently designed do not allow for analytical first derivatives. We are working on this, but for the moment the only way to do an optimization is by brute force finite differences. (Actually, even the gas-phase optimizations are not truly analytical, but they get away with a trick at the NDDO level that fails to be useful for solvation). While this might sound depressing, there is a flip side to the coin. As a rule, reoptimization in solution adds less than 5% to the total solvation free energy relative to that calculated for the gas-phase geometry (the only exception is for very polarizable systems, where small geometrical changes can allow significant distortion of the electronic structure). Many reports in the literature have appeared to this effect by other authors using our models, and we have made these observations too (I'll send you refs if you want, but don't want to waste bandwidth on the net). Since that 5% is typically smaller than the intrinsic error in the model, it is negligible. The frozen geometry calculations only take a few cpu seconds for a system of the size you mentioned, so it is trivial to do the 1SCF calculations, and then decide if you want to invest more time in the full optimization. I add as a final caveat that we are always skeptical about semiempirical geometries after having found time and again some fairly dramatic error in structure (especially intramolecular hydrogen bonds, five-membered rings, amides, and transition states that can exhibit biradicaloid character). Our preferred approach these days is to optimize at a more trustworthy level (depending on your system, that may be anything from a force-field to converged QM calculations) and then add solvation from an SMx calculation at that frozen geometry. In closing, there are electrostatics-only continuum models that permit analytical energy derivatives (e.g., the rather crude Onsager model available in G92 and more refined versions that I believe are slated for release sometime relatively soon, also Tomasi's PCM approach or Rivail's multipole expansion in idealized cavities, coded into GAMESS-UK and the former perhaps in MONSTERGAUSS). If you are dealing with molecules that do not have stationary gas-phase structures (e.g., an amino acid zwitterion) then you might consider such an approach. The virtue of the SMx models, however, is that they have been developed to simultaneously account for non-electrostatic solvation effects, and thus predict solvation free energies that may be compared directly to experiment (Version 4.5 contains only water models, soon-to-be-released version 5.0 also contains hydrocarbon models, other solvents are in various stages of current development). Best regards, Chris P.S. You'll find the above summarized into one sentence in section 8 of the users' manual (which illustrates a nameless universal truth . . . ) -- Christopher J. Cramer University of Minnesota Department of Chemistry 207 Pleasant St. SE Minneapolis, MN 55455-0431 (612) 624-0859 cramer@maroon.tc.umn.edu From semper@tdc.dircon.co.uk Sat Oct 22 09:22:07 1994 Received: from felix.dircon.co.uk for semper@tdc.dircon.co.uk by www.ccl.net (8.6.9/930601.1506) id IAA08274; Sat, 22 Oct 1994 08:38:09 -0400 Received: from semper.dircon.co.uk by felix.dircon.co.uk with SMTP id AA18409 (5.67b/IDA-1.5 for ); Sat, 22 Oct 1994 13:30:41 +0100 Message-Id: <199410221230.AA18409@felix.dircon.co.uk> Sender: From: "Oliver Hill" Organization: Indumabal Handels AG To: CHEMISTRY@ccl.net Date: Sat, 22 Oct 1994 13:35:20 GMT Subject: SUMMARY:Refs for BSSE in MO calcs Reply-To: semper@dircon.co.uk Priority: normal X-Mailer: Pegasus Mail/Windows (v1.22) Earlier this week I posted a request for references on the Basis Set Superposition Error (BSSE). I had many responses which have been most useful to me, thank you very much to all who took the time and trouble to reply. Following is a summary of all replies containing references. Oliver (PS. I'm not a Dr (yet)!!) ------------------------------------------------- Original Posting ------------------- >Dear netters >Please could someone point me to some references (books or papers) >that deal with Basis Set Superposition Errors (BSSE) in Ab Initio >MO calculations. I have been unable to find anything in books so far. >Any help will be greatly appreciated. I will summarize if there is sufficient >interest/responses. >Oliver >PS. I have the postings from 16/17 Oct on BSSE and DFT. Responses ------------- >From Dennis Salahub: Dear Dr. Hill, I happened to be looking at BSSE last night, for a graduate course I am giving. Here are a few refs. that ware handy. "Gaussian Basis sets for Molecular Calculations", S. Huzinaga, Elsevier (1991) "Ab Initio Calculations", P. Carsky and M.Urban, Springer- Verlag, Lecture Notes in Chemistry, 1980. "Intermolecular COmplexes", P. Hobza and R. Zahradnik,Academia, Prague (1988) -the original ref. on counterpoise correction - S.F. Boys and F. Bernardi, Mol. Phys. 19, 553 (1970) -another ref. cited by Huzinaga, about small or medium basis sets: W. Kolos, Theoret. Chim., Acta 51, 219 (1979) Hope these are of some use to you. -Dennis Salahub --------------------------------------------------- >From John Sichel BSSE is discussed briefly in I.N. Levine's Quantum Chemistry 4th edn (Prentice-Hall 1991) p.603, with several references to papers. Also see Tim Clark's Handbook of Computational Chemistry (Wiley 1985) p.289-301, for technical details of specifying the basis using the counterpoise method. John Sichel Universite de Moncton Moncton, NB, CANADA ------------------------------------------------------ >From Donald B. Boyd: Dr. Hill, Steve Scheiner has an excellent chapter in "Reviews in Computational Chemistry," Vol. II, which explains BSSE in relation to hydrogen bonded systems. Reviews in Computational Chemistry is published by VCH Publishers, New York. I will send you further information to your S. African address. ----------------------------------------------------------------- >From Rene Fournier: Hello Oliver, Regarding BSSE, there has been renewed interest and many publications on that topic recently. Here is my bibliography on that, these papers contain many references to earlier work. 1) J. J. Novoa, M. Planas, M.H. Whanbo, Chem. Phys. Lett. 225 (1994) 240. 2) S. Saebo, W. Tong, and P. Pulay, J. Chem. Phys. 98 (1993) 2170. 3) Z. Latajka, S. Scheiner, G. Chalasinski, Chem. Phys. Lett. 196 (1992) 384. 4) D. W. Schwenke and D. G. Truhlar, J. Chem. Phys. 82 (1985) 2418. 5) M. Gutowski and G. Chalasinski, J. Chem. Phys. 98 (1993) 5540. 6) M. Gutowski, J. G.C. M. van Duijneveldt-van de Rijdt, J. H. van Lenthe, and F. B. van Duijneveldt, J. Chem. Phys. 98 (1993) 4728. 7) A. Sadlej, J. Chem. Phys. 95 (1991) 6705. 8) I. Mayer, J. Chem. Phys. 97 (1992) 5257; A. Sadlej, ibid. 5259. 9) S. F. Boys and F. Bernardi, Mol. Phys. 19 (1970) 553. 10) H. B. Jansen and P. Ros, Chem. Phys. Lett. 3 (1969) 140. 11) E. R. Davidson and S. J. Chakravorty, Chem. Phys. Lett 217 (1994) 48. Regards, Rene. ( Note: Among the following references, I particularly like Ref. No. 11, I find it clear and straight to the point. ) #-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-# # Rene Fournier # # Institut Steacie des sciences moleculaires # # Conseil national de la recherche # # 100 Sussex Drive # # Ottawa, Ontario, Canada K1A 0R6 # # # # tel. : 613 990 0964 # # e-mail : fournie@ned1.sims.nrc.ca # # FAX : 613 954 5242 # #-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-#-# ---------------------------------------------------------------------- >From Agnieszka Abkowicz: Hello, Try to find some information in: Beyer A, Karpfen A,Schuster P,Top Current Chem.,120,1,(1984). Urban M.,Hobza P.,Theor.Chim.Acta.,36,207,215(1975). Bulski H., Chalasinski G.,ibid.,44,399,(1977) Kolos W.,ibid.,51,219(1979) Ostlund N.S.,Merrifield D.L,Chem.Phys.Lett.,39,612,(1976) Wells B.H., Wilson S., ibid.,101,429,(1983) Leclercq J.M.,Allavena M., Bouteiller Y.,J.Chem.Phys,78,4606(1983) Kurdi J., Kochanski E.,Diercksen G.H.F., Chem.Phys.,92,287(1985) Boys S.F., Bernardi F., Mol.Phys.,19,553,(1970) Johansson A.,Kollman P.,RothenbergS., Theor.Chim.Acta,29,167,(1973) Morokuma K., Kitaura K in Chemical Applications of Atomic and Molecular Electrostatic Potentials Truhlar D, Politzer P, Eds., Plenum,New York,1981,pp.215-242. Schwenke D.W. , Truhlar D.G., J.Chem. Phys.,82,2418(1985) Dacre P.D., Chem.Phys.Lett.50,147(1977) Mol.Phys. 37,1529(1979) Price S.L,Stone A.J, Chem.Phys Lett,65,127(1979) Spiegelmann F., Malrieu J.P.,Mol.Phys.,40,1273(1980) Newton M.D., Kestner N.R.,Chem.Phys.Lett.,94,198,(1983) Wells B.H.,Wilson S., Mol.Phys.,50,1295(1983);54,787(1985) van Lenthe J.H., van Dam T.,van Duijneveldt F.B.,Faraday Symp.Chem.soc.19,125(1984) Latajka Z.,Scheiner S.,Chem. Phys., 98,59(1985) Baum J.O.,Finney j.L., Mol.Phys.,55,1097,(1985) Latajka Z., Scheiner S.,Chem.Phys.Lett.,105,435(1984) Latajka Z., Scheiner S., J.Comp.Chem.8,663,(1987) Alagona G.,Ghio C.,Latajka Z.,Tomasi J.,J.Phys.Chem,94,2267(1990) Davidson E.R.,Feller D,Chem.Rev.,86,681(1986) and so on.Good luck. I'll appreciate for summary of this subject. Agnieszka ----------------------------------------------------------------- >From Cory C. Pye See our paper, C. C. Pye, R. A. Poirier, D. Yu, P. R. Surjan, {\em J. Mol. Struct. (Theochem)}, {\bf 307} (1994) pp239-259 and practically anything by I. Mayer (see references from above). Some of his recent work includes Chem. Phys. Letters 224 (1994) p 166 ************* ***************** ! Cory C. Pye *** ** ** ** ! Graduate Student ** * **** ! Unpaid Sys Admin ** * * ! Theoretical and ** * * ! Computational Chemistry *** * * ** ! ***************** ! Les Hartree-Focks ************* ! (Apologies to Montreal Canadien Fans) ----------------------------------------------------------------------- >From Teerakiat Kerdcharoen (NOY): Hallo, I may give .... 1)Behera, L., Kar, T., and Sannigrahi, A.B. (1990). Effect of basis-set superposition on the atomic charges and valencies in hydrogen- and lithium-bonded complexes. Chem. Phys. Lett. 172, 487-493. This paper compares two methods for basis set superposition error corrections, namely CP (counterpoise) method invented by Boys and Bernadi and PCP (polarization counterpoise) method which takes only unoccupied orbitals as ghost orbitals. 2)Chalasinski, G., Funk, D.J., Simons, J., and Breckenridge, W.H. (1987). Moller-Plesset perturbation theory for van der Waals complexes bound by electron correlation effects: Ground states of the Ar and Mg dimers. J. Chem.Phys. 87, 3569-3579. This paper remarks how significant BSSE is in correlated level. The authors encourage the use of CP method as a resolution and well-tempered basis set to reduce BSSE. 3)Hassett, D.M., Marsden, C.J., and Smith, B.J. (1991). The ammonia dimer potential energy surface: resolution of the apparent discrepancy between theory and experiment ? Chem. Phys. Lett. 183, 449-456. This is a good example of how BSSE has created inconsistent calculation results of ammonia system. 4)Hobza, P. and Zahradnik, R. (1988). Intermolecular interactions between medium-sized systems. Nonempirical and empirical calculations of interaction energies: Success and failures. Chem. Rev. 88, 871-897. A timely review on MO calculation and its obstacles. 5)Kurdi, L., Kochanski, E., and Diercksen, G.H.F. (1985). Determination of the basis set superposition error with "DZP" basis sets in SCF calculations: CO + H2. NH3 + H2, H2 + H2. Chem. Phys. 92, 287-294. The paper shows the success of counterpoise method as the best way to go for BSSE correction. take care, Teerakiat ---------------------------------------------------------------------------- Teerakiat Kerdcharoen (NOY) Institute of General and Inorganic and Theoretical Chemistry Innrain 52a, A-6020 Innsbruck AUSTRIA e-mail: noy@tci2.uibk.ac.at, noy@tci.uibk.ac.at, c72454@cx.uibk.ac.at : noy@atc.atccu.chula.ac.th, noy@atc2.atccu.chula.ac.th ( Bangkok ) Research : Molecular Dynamics simulations : Computer Aided Molecular/Material Designs ----------------------------------------------------------------------------- *** I have no past and no future. I just have today. ----------------------------------------------------------------------- >From Jan Hrusak: Dear Oliver, [stuff deleted] BSSE : Boys, Bernardi, Mol. Phys. 19 (1970) 553 Jan --------------------------------------------------------------------- >From Magan Govender: HI, There is a reference in Mol. Physics.,19 (1970) 53, bye S.F Boys and F.Bernardi REgards ______________________________________________________________________ M.G. Govender Centre for Theoretical and Computational Chemistry Dept of Chemistry University of Natal King George V Avenue Durban South Africa ---------------------------------------------------------------------- ______________________________________________________________________ | Oliver Hill | | | Department of Chemistry | "The true scientist never | | University of Cape Town | loses the faculty of | | Rondebosch, 7700 | amazement. It is the essence | | SOUTH AFRICA | of his(her) being." | | E-Mail:oliver@psipsy.uct.ac.za | - HANS SELYE | |--------------------------------------------------------------------| | Contact until 24 October 1994 | | | | E-Mail: semper@dircon.co.uk 1 Belgrave Place | | Tel. +44-71-235-8197 London SW1X 8BU | | Fax. +44-71-823-2112 UNITED KINGDOM | |____________________________________________________________________| From semper@tdc.dircon.co.uk Sat Oct 22 12:22:09 1994 Received: from felix.dircon.co.uk for semper@tdc.dircon.co.uk by www.ccl.net (8.6.9/930601.1506) id LAA09289; Sat, 22 Oct 1994 11:22:48 -0400 Received: from semper.dircon.co.uk by felix.dircon.co.uk with SMTP id AA21231 (5.67b/IDA-1.5 for ); Sat, 22 Oct 1994 16:15:23 +0100 Message-Id: <199410221515.AA21231@felix.dircon.co.uk> Sender: From: "Oliver Hill" Organization: Indumabal Handels AG To: CHEMISTRY@ccl.net Date: Sat, 22 Oct 1994 16:18:37 GMT Subject: SUMMARY ADDITION: Refs for BSSE in MO calcs Reply-To: semper@dircon.co.uk Priority: normal X-Mailer: Pegasus Mail/Windows (v1.22) This message should be appended to the summary I posted earlier. Sorry about the wasted bandwidth but this message was sent to my South African address, and I only retrieved it today! Oliver ----------------------------------------------------------- >From Janet Del Bene: There has been a lengthy discussion in the literature concerning BSSE and its correction. I have two recent papers which address this problem. J. E. Del Bene, Int. J. Quantum Chem. Quantum Chem. Symp. 26, 527 (1992). J. E. Del Bene, J. Phys. Chem. 97, 107 (1993). You should also consult papers by Frisch, Schaeffer, Truhlar, and Scheiner. Hope this helps. QUIT  ______________________________________________________________________ | Oliver Hill | | | Department of Chemistry | "The true scientist never | | University of Cape Town | loses the faculty of | | Rondebosch, 7700 | amazement. It is the essence | | SOUTH AFRICA | of his(her) being." | | E-Mail:oliver@psipsy.uct.ac.za | - HANS SELYE | |--------------------------------------------------------------------| | Contact until 24 October 1994 | | | | E-Mail: semper@dircon.co.uk 1 Belgrave Place | | Tel. +44-71-235-8197 London SW1X 8BU | | Fax. +44-71-823-2112 UNITED KINGDOM | |____________________________________________________________________|