From MAILER-DAEMON@www.ccl.net Mon Jul 22 11:15:40 1996 Received: from mail-relay-BLR.ernet.in for MAILER-DAEMON@www.ccl.net by www.ccl.net (8.7.5/950822.1) id KAA15659; Mon, 22 Jul 1996 10:21:56 -0400 (EDT) Received: from postoffice.iisc.ernet.in (twisha.ece.iisc.ernet.in [144.16.64.4]) by mail-relay-BLR.ernet.in (8.6.11/8.6.9) with ESMTP id TAA20685 for ; Mon, 22 Jul 1996 19:01:02 +0530 Received: by postoffice.iisc.ernet.in (SMI-8.6/SMI-SVR4) id TAA11580; Mon, 22 Jul 1996 19:54:20 -0500 Date: Mon, 22 Jul 1996 19:54:20 -0500 From: ipcakc@Postoffice (Dr.A.K.Chandra) Message-Id: <199607230054.TAA11580@postoffice.iisc.ernet.in> To: CHEMISTRY@www.ccl.net Subject: G94: G94/DFT/Tr.State Problem Dear Netters, I found some funny problem using B3LYP/6-31G** keyword for the following transition state. It is a H-transfer process between two Cl atoms forming a symmetric transition state Cl---------H---------Cl with equal bond lengths. The Geometry optimisation leads to a perfectly symmetric structure (B3lyp/6-31G**/UHF). The system is a doublet and is a radical-molecule reaction. Now, the fun is that the eigenvalue corresponding to the imaginary frequency at the saddle point is ONLY ONE. But, if the frequencies are seen, there are 3 IMAGINARY FREQUENCIES. The Keyword I have used for optimisation of transition state is OPT=(TS,EF,CALCALL), hence frequency calculation is done along with the optimisation. The output is attached below. Can anyone help me in interpreting this result? Sincerely, V. Sreedhara Rao. -------------------------------------------- V. Sreedhara Rao Department of IPC, Indian Institute of Science, BANGALORE - 560 012. INDIA. E-mail : ipcakc@postoffice.iisc.ernet.in -------------------------------------------- ------------------------The output follows ---------------------- ********************************************** Gaussian 94: IBM-RS6000-G94RevC.2 5-Aug-1995 12-Jul-1996 ********************************************** ----------------------------------------------------------- #uhf 6-31g** opt=(ef,ts,calcall) b3lyp pop=full den=current ----------------------------------------------------------- EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF- ------------------------------------------------------------------------ Z-MATRIX (ANGSTROMS AND DEGREES) CD Cent Atom N1 Length/X N2 Alpha/Y N3 Beta/Z J ------------------------------------------------------------------------ 1 1 Cl 2 2 H 1 1.497666( 1) 3 X 2 1.000000( 2) 1 90.000( 4) 4 3 Cl 2 1.497673( 3) 3 90.000( 5) 1 180.000( 6) 0 ------------------------------------------------------------------------ SCF Done: E(UB+HF-LYP) = -920.925868655 A.U. after 13 cycles Convg = .7439D-08 -V/T = 2.0030 S**2 = .7571 Annihilation of the first spin contaminant: S**2 before annihilation .7571, after .7500 EIGENVECTOR FOLLOWING TRANSITION STATE SEARCH ANALYTICAL SECOND DERIVATIVES USED ITERATION 3 EIGENVECTORS AND EIGENVALUES 1 2 EIGENVALUES -- -.02252 .16489 1 R1 -.70710 .70711 2 R2 .70711 .70710 TS SEARCH. TAKING P-RFO STEP SEARCHING FOR LAMDA THAT MAXIMIZES ALONG THE LOWEST MODE VALUE TAKEN LAMDA= .00000000 SEARCHING FOR LAMDA THAT MINIMIZES ALONG ALL OTHER MODES VALUE TAKEN LAMDA= .00000000 STEP TAKEN. STEPSIZE IS .000014 CURRENT PARAMETER VALUES (INTERNAL COORDINATES) I X GRADIENT DISPLACEMENT NEWX 1 2.830179 -.000001 .000014 2.830193 2 2.830192 -.000001 .000001 2.830193 ITEM VALUE THRESHOLD CONVERGED? MAXIMUM FORCE .000001 .000450 YES RMS FORCE .000001 .000300 YES MAXIMUM DISPLACEMENT .000014 .001800 YES RMS DISPLACEMENT .000010 .001200 YES ************************************************* ** CONVERGENCE CRITERIA APPARENTLY SATISFIED ** ************************************************* ---------------------------- ! Optimized Parameters ! ! (Angstroms and Degrees) ! ---------------------- ---------------------- ! Name Value Derivative information (Atomic Units) ! ------------------------------------------------------------------------ ! R1 1.4977 -DE/DX = 0. ! ! R2 1.4977 -DE/DX = 0. ! ------------------------------------------------------------------------ PREDICTED CHANGE IN ENERGY .000000 EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF-EF- ------------------------------------------------------------------------ Z-MATRIX (ANGSTROMS AND DEGREES) CD Cent Atom N1 Length/X N2 Alpha/Y N3 Beta/Z J ------------------------------------------------------------------------ 1 1 Cl 2 2 H 1 1.497666( 1) 3 X 2 1.000000( 2) 1 90.000( 4) 4 3 Cl 2 1.497673( 3) 3 90.000( 5) 1 180.000( 6) 0 ------------------------------------------------------------------------ Exact polarizability: 14.928 .000 14.928 .000 .000 53.183 Approx polarizability: 15.126 .000 15.126 .000 .000 79.255 Rotating electric field derivatives to standard orientation. Rotating nuclear coordinate derivatives to standard orientation. Full mass-weighted force constant matrix: Low frequencies ----1517.7789-1517.7789-1094.5308 -.0078 -.0064 -.0064 Low frequencies --- 7.4380 7.4380 352.9932 ****** 3 imaginary frequencies (negative signs) ****** Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering activities (A**4/AMU), Raman depolarization ratios, reduced masses (AMU), force constants (mDyne/A) and normal coordinates: 1 2 3 PI PI SG Frequencies -- -1517.7789 -1517.7789 -1094.5308 Red. masses -- 1.0219 1.0219 1.0219 Frc consts -- 1.3870 1.3870 .7213 IR Inten -- 460.3973 460.3973 446.2129 Raman Activ -- .0000 .0000 .0000 Depolar -- .0000 .0000 .0000 Atom AN X Y Z X Y Z X Y Z 1 17 -.01 .00 .00 .00 -.01 .00 .00 .00 -.01 2 1 1.00 .00 .00 .00 1.00 .00 .00 .00 1.00 3 17 -.01 .00 .00 .00 -.01 .00 .00 .00 -.01 4 SG Frequencies -- 352.9932 Red. masses -- 34.9689 Frc consts -- 2.5672 IR Inten -- .0000 Raman Activ -- .0000 Depolar -- .0000 Atom AN X Y Z 1 17 .00 .00 .71 2 1 .00 .00 .00 3 17 .00 .00 -.71 ------------------- - Thermochemistry - ------------------- Temperature 298.150 Kelvin. Pressure 1.00000 Atm. Atom 1 has atomic number 17 and mass 34.96885 Atom 2 has atomic number 1 and mass 1.00783 Atom 3 has atomic number 17 and mass 34.96885 Molecular mass: 70.94553 amu. Principle axes and moments of inertia in atomic units: 1 2 3 EIGENVALUES -- .00000 560.19741 560.19741 X .00000 .00000 1.00000 Y .00000 1.00000 .00000 Z 1.00000 .00000 .00000 THIS MOLECULE IS A PROLATE SYMMETRIC TOP. ROTATIONAL SYMMETRY NUMBER 1. WARNING-- ASSUMPTION OF CLASSICAL BEHAVIOR FOR ROTATION MAY CAUSE SIGNIFICANT ERROR ROTATIONAL TEMPERATURE (KELVIN) .15461 ROTATIONAL CONSTANT (GHZ) 3.221616 3 IMAGINARY FREQUENCIES IGNORED. Zero-point vibrational energy 2111.4 (Joules/Mol) .50463 (Kcal/Mol) WARNING-- EXPLICIT CONSIDERATION OF 1 DEGREES OF FREEDOM AS VIBRATIONS MAY CAUSE SIGNIFICANT ERROR VIBRATIONAL TEMPERATURES: 507.88 (KELVIN) Zero-point correction= .000804 (Hartree/Particle) Thermal correction to Energy= .003523 Thermal correction to Enthalpy= .004467 Thermal correction to Gibbs Free Energy= -.023207 Sum of electronic and zero-point Energies= -920.925064 Sum of electronic and thermal Energies= -920.922346 Sum of electronic and thermal Enthalpies= -920.921402 Sum of electronic and thermal Free Energies= -920.949076 E CV S KCAL/MOL CAL/MOL-KELVIN CAL/MOL-KELVIN TOTAL 2.210 6.537 58.245 ELECTRONIC .000 .000 1.377 TRANSLATIONAL .889 2.981 38.695 ROTATIONAL .592 1.987 17.019 VIBRATIONAL .729 1.569 1.153 VIBRATION 1 .729 1.569 1.153 Q LOG10(Q) LN(Q) TOTAL BOT .472556D+11 10.674453 24.377872 TOTAL V=0 .110751D+12 11.044347 25.229583 VIB (BOT) .521657D+00 -.282615 -.650746 VIB (BOT) 1 .521657D+00 -.282615 -.650746 VIB (V=0) .122258D+01 .087278 .200965 VIB (V=0) 1 .122258D+01 .087278 .200965 ELECTRONIC .200000D+01 .301030 .693147 TRANSLATIONAL .234881D+08 7.370848 16.972005 ROTATIONAL .192837D+04 3.285191 7.564431 Internal Forces: Max .000001377 RMS .000000714 1\1\GINC-IBM580_7\Freq\UB3LYP\6-31G(d,p)\Cl2H1(2)\IPCVSR\12-Jul-1996\1 \\#UHF 6-31G** OPT=(EF,TS,CALCALL) B3LYP POP=FULL DEN=CURRENT\\clhcl-1 .6 ang.\\0,2\Cl\H,1,R1\X,2,1.,1,90.\Cl,2,R2,3,90.,1,180.,0\\R1=1.49766 611\R2=1.49767315\\Version=IBM-RS6000-G94RevC.2\State=2-SG\HF=-920.925 8687\S2=0.757\S2-1=0.\S2A=0.75\RMSD=7.439e-09\RMSF=5.912e-07\Dipole=0. ,0.,0.0000045\DipoleDeriv=-0.3424881,0.,0.,0.,-0.3424881,0.,0.,0.,0.33 71667,0.684973,0.,0.,0.,0.684973,0.,0.,0.,-0.6743387,-0.3424849,0.,0., 0.,-0.3424849,0.,0.,0.,0.3371721\Polar=14.9278148,0.,14.9278148,0.,0., 53.1825654\PG=C*V [C*(Cl1H1Cl1)]\NImag=3\\-0.02161655,0.,-0.02161655,0 .,0.,0.07118866,0.04330625,0.,0.,-0.08661238,0.,0.04330625,0.,0.,-0.08 From ccl@www.ccl.net Mon Jul 22 20:15:46 1996 Received: for ccl@www.ccl.net by www.ccl.net (8.7.5/950822.1) id UAA19080; Mon, 22 Jul 1996 20:04:00 -0400 (EDT) From: Computational Chemistry Message-Id: <199607230004.UAA19080@www.ccl.net> Subject: UFF To: chemistry@www.ccl.net Date: Mon, 22 Jul 1996 20:04:00 -0400 (EDT) X-Mailer: ELM [version 2.4 PL23] MIME-Version: 1.0 Content-Type: text/plain; charset=US-ASCII Content-Transfer-Encoding: 7bit > >From schlecmf@esvax.dnet.dupont.com Mon Jul 22 10:15:41 1996 > Received: from gatekeeper.es.dupont.com for schlecmf@esvax.dnet.dupont.com > by www.ccl.net (8.7.5/950822.1) id JAA15439; Mon, 22 Jul 1996 09:20:08 -0400 (EDT) > From: > Received: by gatekeeper.es.dupont.com; id JAA02231; Mon, 22 Jul 1996 09:20:09 -0400 > Received: by esds01.es.dupont.com; id AA21661; Mon, 22 Jul 96 09:20:00 -0400 > Message-Id: <9607221320.AA21661@esds01.es.dupont.com> > Received: from esvax.dnet; by esds01.dnet; Mon, 22 Jul 96 09:20:08 EDT > Date: Mon, 22 Jul 96 09:20:08 EDT > To: chemistry@www.ccl.net > Apparently-To: chemistry@www.ccl.net > Subject: CCL: Re: UFF > > > Peter: > > I just got notification from the automated current awareness WWWeb utility > at Amazon Books (http://www.amazon.com/) about a soon-to-publish book by Rappe > and Casewit which is very likely concerned to some extent with Rappe's > Universal Force Field: > ---------------------------------------------- > "Molecular Mechanics Across Chemistry," by Anthony K. Rappe , Carla J. Casewit > > Hardcover > Price information not available. > Published by Univ Science Books > Publication date: August 1996 > ISBN: 0935702776 > > Not Yet Available: > ---------------------------------------------- > This information (and capability of ordering) is found at: > > http://www.amazon.com/exec/obidos/ISBN=0935702776 > > I've seen Rappe give talks on the subject at some recent ACS meetings. > Some authors are referring to Halgren's new Merck Molecular Force Field > (MMFF94) as a/the UFF. There are also references to UFF which concern the > "Universality of Free Fall" in the study of interplanetary matter, and to > Urea-Formaldehyde Fertilizer, both of which are probably of little interest. > Following are a few recent references which I believe are specifically > concerned with Rappe's UFF. > > Anal. Sci. Technol. (1995), 8(4), 519-27. [Chem. Abstr. 124:305980] > Macromolecules (1995), 28(22), 7370-5. [Chem. Abstr. 123 229465] > J. Am. Chem. Soc. (1995), 117(23), 6194-8. [Chem. Abstr. 123 55409] > J. Mol. Struct. (1994), 323(1-3), 93-101. [Chem. Abstr. 121 120549] > Inorg. Chim. Acta (1993), 213(1-2), 319-24. [Chem. Abstr. 120 4998] > Inorg. Chem. (1993), 32(16), 3438-50. [Chem. Abstr. 119 80553] > > Hope this helps. > > Matthew F. Schlecht > DuPont Agricultural Products > Newark, DE 19714-0030 USA > schlecmf@esvax.dnet.dupont.com >