From chemistry-request@server.ccl.net Wed Feb 21 05:57:04 2001 Received: from marvin.cup.uni-muenchen.de (root@marvin.cup.uni-muenchen.de [141.84.253.2]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1LAumw15323 for ; Wed, 21 Feb 2001 05:57:04 -0500 Sender: tmehnert@cup.uni-muenchen.de Message-ID: <3A93ABE8.A642A74B@cup.uni-muenchen.de> Date: Wed, 21 Feb 2001 12:52:08 +0100 From: Thomas Mehnert X-Mailer: Mozilla 4.76 [en] (X11; U; Linux 2.2.14 i686) X-Accept-Language: en MIME-Version: 1.0 To: chemistry@ccl.net Subject: CASSCF - Memory Problem Content-Type: text/plain; charset=us-ascii Content-Transfer-Encoding: 7bit Hello everybody, It seems Gaussian has no will to reply my questions so if you can help me please do it. I tried to calculate some molecules like butadiene with CASSCF. So I am interested in searching conical intersections and higher excited electronical states. But unfortunately my jobs always crash because of insufficient memory. Attached below you find the last part of the output of a crashed job. I even increased the Memory allocation up to 900MB but without any success. Do you know any keywords (or a combination of keywords) or something like this to prevent these error terminations? Thanks in advance Thomas Mehnert . . . . 34 SYMMETRY TYPE = 0 3 4 2 4 35 SYMMETRY TYPE = 0 2 4 3 4 36 SYMMETRY TYPE = 0 3 4 3 4 NO OF BASIS FUNCTIONS = 36 NO TO BE DELETED = 0 CI Matrix Elements calculated here NO. OF CONFIGURATIONS IN REFERENCE SPACE = 1 SECONDARY SPACE = 36 TERTIARY SPACE = 36 NO. OF ORBITALS = 4 NO. OF ELECTRONS = 4 NO. OF WEIGHTS = 9 REFERENCE STATE CONFIGURATIONS ARE: 0 NO. OF CORE ORBITALS = 0 OPTION: NON-DIAGONAL HOLE LINE INTERACTIONS INCLUDED Len28= 4455 LenMCI= 2252. Leave Link 405 at Tue Feb 6 16:55:27 2001, MaxMem= 6291456 cpu: .9 (Enter /usr/local/gaussian/g98/l510.exe) MCSCF will prepare Gradient Dif. and Deriv. Cps. ENTER MCSCF PROGRAM NO. OF ORBITALS =106 NO. OF CORE-ORBITALS = 13 NO. OF VALENCE-ORBITALS = 4 NO. OF VIRTUAL-ORBITALS = 89 USED ACCURACY IN CHECKING CONVEGERGENCE = 1.00D-08 Memory needed for direct integral evaluation: 9921927 INCORE Storage needs space: 29617248 INCORE Storage exept BETA : 16345100 INCORE SORTING needs space: 16345100 DISK based calculation Calculation does not fit in Transformation Increase the memory to: 8546728 Error termination via Lnk1e in /usr/local/gaussian/g98/l510.exe. Job cpu time: 0 days 0 hours 0 minutes 39.3 seconds. File lengths (MBytes): RWF= 10 Int= 158 D2E= 0 Chk= 6 Scr= 1 From chemistry-request@server.ccl.net Wed Feb 21 10:29:13 2001 Received: from judy.ic.ac.uk (judy.ic.ac.uk [155.198.5.28]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1LFTCw17639 for ; Wed, 21 Feb 2001 10:29:12 -0500 Received: from juliet.ic.ac.uk ([155.198.5.4]) by judy.ic.ac.uk with esmtp (Exim 2.12 #1) id 14VbCd-0001BZ-00 for chemistry@ccl.net; Wed, 21 Feb 2001 15:29:15 +0000 Received: from sunfs1-gw.ps.ic.ac.uk ([155.198.164.2] helo=sunfs1.ps.ic.ac.uk) by juliet.ic.ac.uk with esmtp (Exim 2.12 #1) id 14VbCv-0005YU-00 for chemistry@ccl.net; Wed, 21 Feb 2001 15:29:33 +0000 Received: from sunv44.ps.ic.ac.uk by sunfs1.ps.ic.ac.uk (8.8.8+Sun/4.1) id PAA07008; Wed, 21 Feb 2001 15:29:14 GMT From: aileen.cheung@ic.ac.uk Date: Wed, 21 Feb 2001 15:29:12 GMT Message-Id: <26099.200102211529@sunv44.ps.ic.ac.uk> To: chemistry@ccl.net Subject: BOSS Z-matrix Mime-Version: 1.0 Content-Type: text/plain; charset=us-ascii Content-Transfer-Encoding: 7bit Content-MD5: cEHCr5KdH/h8XqcGCWFgww== Hello, I would like to minimise a pair of butane / ethylamine molecules using the OPLS force field using the BOSS z-matrix attached below. However using the z-matrix form below, the program does not seem to account for the nonbonded distances between the separate molecules. On the other hand, if I remove the TERZ sentence separating the molecules, the program then regards the two molecules to be bonded together. I would appreciate any help in correcting the z-matrix. Thank you in advance. Regards, Aileen BOSS Z-Matrix 1 X -1 0 0 0.000000 0 0.00000 0 0.00000 0 2 X -1 0 1 1.000000 0 0.00000 0 0.00000 0 3 C2 136 136 2 1.000000 1 90.00000 0 0.00000 0 4 C3 136 136 3 1.532001 2 62.51995 1 -115.96822 0 5 C4 135 135 3 1.529407 2 90.00000 4 115.96822 0 6 HC 140 140 3 1.104539 4 109.40421 5 121.77148 0 7 HC 140 140 3 1.104128 4 109.33929 6 116.50861 0 8 C1 135 135 4 1.528855 3 112.89172 5 179.93024 0 9 HC 140 140 4 1.104828 3 109.28656 8 121.90598 0 10 HC 140 140 4 1.104710 3 109.25882 8 -121.86766 0 11 HC 140 140 8 1.102362 4 110.91327 3 60.26271 0 12 HC 140 140 8 1.102340 4 111.30114 11 119.92243 0 13 HC 140 140 8 1.101220 4 110.93799 11 -120.13919 0 14 HC 140 140 5 1.102524 3 110.87946 4 59.94911 0 15 HC 140 140 5 1.101120 3 111.35493 14 120.05918 0 16 HC 140 140 5 1.101545 3 110.90141 14 -119.83681 0 TERZ 17 CT 906 906 7 3.191532 3 128.56883 4 -112.80909 0 18 HC 140 140 7 2.696665 3 99.76369 17 -34.89651 0 19 HC 140 140 7 4.263866 3 105.54533 17 -21.36044 0 20 HC 140 140 7 3.898963 3 122.41349 17 -41.25748 0 21 CT 135 135 17 1.524068 7 83.48002 3 -65.16467 0 22 NT 900 900 17 1.457853 7 80.33909 21 111.18851 0 23 HC 911 911 17 1.106196 7 54.34464 21 -119.69638 0 24 HC 911 911 17 1.103723 7 160.51586 21 -128.75974 0 25 H2 909 909 22 1.003409 17 110.47635 7 -14.74441 0 26 H2 909 909 22 1.002610 17 111.78115 25 118.38537 0 Geometry Variations follow (2I4,F12.6) Variable Bonds follow (I4) 0004-0026 Additional Bonds follow (2I4) 21 18 21 19 21 20 Harmonic Constraints follow (2I4,4F10.4) Variable Bond Angles follow (I4) 0005-0026 Additional Bond Angles follow (3I4) AUTO Variable Dihedrals follow (3I4,F12.6) 0006-0026 Additional Dihedrals follow (6I4) AUTO Domain Definitions follow (4I4) Conformational Search (2I4,2F12.6) Final blank line From chemistry-request@server.ccl.net Wed Feb 21 10:44:07 2001 Received: from pollux.chem.umn.edu (pollux.chem.umn.edu [128.101.156.56]) by server.ccl.net (8.11.0/8.11.0) with ESMTP id f1LFi7w17745 for ; Wed, 21 Feb 2001 10:44:07 -0500 Received: (from cramer@localhost) by pollux.chem.umn.edu (8.9.3/8.9.3) id JAA01667 for CHEMISTRY@ccl.net; Wed, 21 Feb 2001 09:44:01 -0600 (CST) From: Christopher Cramer Message-Id: <200102211544.JAA01667@pollux.chem.umn.edu> Subject: Koopmans' theorem, heat, and light To: CHEMISTRY@ccl.net Date: Wed, 21 Feb 2001 09:44:01 -0600 (CST) X-Mailer: ELM [version 2.5 PL2] MIME-Version: 1.0 Content-Type: text/plain; charset=us-ascii Content-Transfer-Encoding: 7bit The ongoing discussion has generated more of the second and less of the third with respect to the first. If I may: Koopmans' "theorem" states that, if you take a closed-shell wave function expressed as a single Slater determinant, and either remove an electron > from the highest occupied orbital or add an electron to the lowest virtual orbital, then the new singly occupied orbital is stable with respect to any subsequent variation involving the unoccupied orbitals. This is a rigorous mathematical proof, and as such qualifies as a theorem. Note that, the theorem does NOT say that the remaining DOUBLY occupied orbitals are stable with respect to variation. Nevertheless, Koopmans' "approximation" says, let's compare the energies of the original closed-shell and newly formed open-shell determinants where all doubly-occupied MOs are identical. The difference in the energies is exactly the orbital energy of the singly-occupied orbital. Since that orbital is either the HOMO or the LUMO, depending on whether we ionized or attached, these energies are also called -IP and EA, respectively. As has correctly been pointed out in an earlier post, Koopmans' approximation works much better for IP because failure to account for relaxation effects (which stabilize the radical cation) are offset by failure to account for electron correlation (which preferentially stablizes the closed-shell system as it has more electrons) and finite basis set limitations. EAs are usually very bad from Koopmans' approximation. To be explicit, the relaxation effect is the energy gained from allowing the doubly-occupied orbitals to be variationally optimized in the open-shell system (and, of course, the singly-occupied simultaneously). Determining an IP or EA by this method is sometimes called a "delta-SCF" approach. In the absence of including electron correlation effects and saturating the basis set, this may or may not improve on the Koopmans' estimate. As for DFT, it has been shown, again with complete rigor, that the energy of the highest Kohn-Sham orbital for a closed-shell system is PRECISELY the negative of the ionization potential WHEN THE EXACT FUNCTIONAL IS USED. As everyone knows, that exact functional remains somewhat elusive, so the actual quality of KS eigenvalues for estimating IPs is variable, depending on choice of approximate functional. Thanks for participating in this pedagogical moment. Chris -- Below are our temporary addresses during our sabbatical year in Barcelona (July 23, 2000 - August 1, 2001). Chris at Univ. of Barcelona Cramer Family in Barcelona --------------------------- -------------------------- c/o Professor Javier Luque Via Augusta 228 4/3 Fac. Farmacia, Dept. Fis. Quim. 08021 Barcelona Universitat de Barcelona SPAIN Joan XXIII, s/n Phone: (34) 93 209 4776 08028 Barcelona SPAIN Phone (my mobile): (34) 62 043 1176 Permanent data: Christopher J. Cramer University of Minnesota Department of Chemistry 207 Pleasant St. SE Minneapolis, MN 55455-0431 -------------------------- Phone: (612) 624-0859 || FAX: (612) 626-2006 cramer@pollux.chem.umn.edu http://pollux.chem.umn.edu/~cramer