Default is to use a total of 8 processors: 8 via shared-memory 1 via Linda Entering Link 1 = C:\G09W\l1.exe PID= 8100. Copyright (c) 1988,1990,1992,1993,1995,1998,2003,2009,2013, Gaussian, Inc. All Rights Reserved. This is part of the Gaussian(R) 09 program. It is based on the Gaussian(R) 03 system (copyright 2003, Gaussian, Inc.), the Gaussian(R) 98 system (copyright 1998, Gaussian, Inc.), the Gaussian(R) 94 system (copyright 1995, Gaussian, Inc.), the Gaussian 92(TM) system (copyright 1992, Gaussian, Inc.), the Gaussian 90(TM) system (copyright 1990, Gaussian, Inc.), the Gaussian 88(TM) system (copyright 1988, Gaussian, Inc.), the Gaussian 86(TM) system (copyright 1986, Carnegie Mellon University), and the Gaussian 82(TM) system (copyright 1983, Carnegie Mellon University). Gaussian is a federally registered trademark of Gaussian, Inc. This software contains proprietary and confidential information, including trade secrets, belonging to Gaussian, Inc. This software is provided under written license and may be used, copied, transmitted, or stored only in accord with that written license. The following legend is applicable only to US Government contracts under FAR: RESTRICTED RIGHTS LEGEND Use, reproduction and disclosure by the US Government is subject to restrictions as set forth in subparagraphs (a) and (c) of the Commercial Computer Software - Restricted Rights clause in FAR 52.227-19. Gaussian, Inc. 340 Quinnipiac St., Bldg. 40, Wallingford CT 06492 --------------------------------------------------------------- Warning -- This program may not be used in any manner that competes with the business of Gaussian, Inc. or will provide assistance to any competitor of Gaussian, Inc. The licensee of this program is prohibited from giving any competitor of Gaussian, Inc. access to this program. By using this program, the user acknowledges that Gaussian, Inc. is engaged in the business of creating and licensing software in the field of computational chemistry and represents and warrants to the licensee that it is not a competitor of Gaussian, Inc. and that it will not use this program in any manner prohibited above. --------------------------------------------------------------- Cite this work as: Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2013. ****************************************** Gaussian 09: EM64W-G09RevD.01 13-Apr-2013 20-Nov-2017 ****************************************** %nprocshared=6 Will use up to 6 processors via shared memory. %chk=\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk Default route: MaxDisk=10GB -------------------------------------------------------- # opt freq pm6 geom=connectivity integral=grid=ultrafine -------------------------------------------------------- 1/14=-1,18=20,19=15,26=1,38=1,57=2/1,3; 2/9=110,12=2,17=6,18=5,40=1/2; 3/5=2,16=1,25=1,41=3900000,71=1,75=-5/1,2,3; 4/35=1/1; 5/5=2,35=1,38=5/2; 6/7=2,8=2,9=2,10=2,28=1/1; 7//1,2,3,16; 1/14=-1,18=20,19=15,26=1/3(2); 2/9=110/2; 99//99; 2/9=110/2; 3/5=2,16=1,25=1,41=3900000,71=1,75=-5,135=20/1,2,3; 4/5=5,16=3,35=1/1; 5/5=2,35=1,38=5/2; 7//1,2,3,16; 1/14=-1,18=20,19=15,26=1/3(-5); 2/9=110/2; 6/7=2,8=2,9=2,10=2,19=2,28=1/1; 99/9=1/99; ------------------- Title Card Required ------------------- Symbolic Z-matrix: Charge = 0 Multiplicity = 1 S -0.99071 0.66563 0. O -2.45259 0.81605 0. O 0.45716 0.91743 0. GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Initialization pass. ---------------------------- ! Initial Parameters ! ! (Angstroms and Degrees) ! -------------------------- -------------------------- ! Name Definition Value Derivative Info. ! -------------------------------------------------------------------------------- ! R1 R(1,2) 1.4696 estimate D2E/DX2 ! ! R2 R(1,3) 1.4696 estimate D2E/DX2 ! ! A1 A(2,1,3) 164.26 estimate D2E/DX2 ! -------------------------------------------------------------------------------- Trust Radius=3.00D-01 FncErr=1.00D-07 GrdErr=1.00D-07 Number of steps in this run= 20 maximum allowed number of steps= 100. GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.990712 0.665635 0.000000 2 8 0 -2.452594 0.816049 0.000000 3 8 0 0.457157 0.917429 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.469600 0.000000 3 O 1.469600 2.911517 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.100613 2 8 0 0.000000 -1.455758 -0.100613 3 8 0 0.000000 1.455758 -0.100613 --------------------------------------------------------------------- Rotational constants (GHZ): 780.5242368 7.4546412 7.3841168 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 53.1186423317 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Nonelectrostatic core Hamiltonian diagonalized for initial guess. Initial guess orbital symmetries: Occupied (B2) (A1) (A1) (B2) (B1) (A1) (A2) (B2) (A1) Virtual (B1) (A1) (B1) (A1) (B2) (A2) (A1) (B2) The electronic state of the initial guess is 1-A1. Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. Fock symm off for IB=2 I1= 2 I= 9 J= 1 Cut=1.00D-07 Err=5.90D-03 Fock matrix is not symmetric: symmetry in diagonalization turned off. SCF Done: E(RPM6) = -0.843282233557E-01 A.U. after 15 cycles NFock= 14 Conv=0.36D-08 -V/T= 0.9887 ********************************************************************** Population analysis using the SCF density. ********************************************************************** Orbital symmetries: Occupied (A1) (B2) (A1) (B2) (B1) (A1) (B2) (A2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) The electronic state is 1-A1. Alpha occ. eigenvalues -- -1.11970 -1.09874 -0.75603 -0.55266 -0.54086 Alpha occ. eigenvalues -- -0.53819 -0.42700 -0.42688 -0.35924 Alpha virt. eigenvalues -- -0.03586 -0.03092 0.12568 0.28978 0.30879 Alpha virt. eigenvalues -- 0.30883 0.33345 0.33720 Condensed to atoms (all electrons): 1 2 3 1 S 4.929520 0.000000 0.000000 2 O 0.000000 6.535240 0.000000 3 O 0.000000 0.000000 6.535240 Mulliken charges: 1 1 S 1.070480 2 O -0.535240 3 O -0.535240 Sum of Mulliken charges = 0.00000 Mulliken charges with hydrogens summed into heavy atoms: 1 1 S 1.070480 2 O -0.535240 3 O -0.535240 Charge= 0.0000 electrons Dipole moment (field-independent basis, Debye): X= 0.0000 Y= 0.0000 Z= 0.6211 Tot= 0.6211 N-N= 5.311864233173D+01 E-N=-8.731139131366D+01 KE=-7.455934158123D+00 Symmetry A1 KE=-3.701076493408D+00 Symmetry A2 KE=-4.306882725418D-01 Symmetry B1 KE=-6.267822900546D-01 Symmetry B2 KE=-2.697387102119D+00 Calling FoFJK, ICntrl= 2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 -0.000322865 0.009266727 0.000000000 2 8 0.076861569 -0.001961025 0.000000000 3 8 -0.076538704 -0.007305702 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.076861569 RMS 0.036376228 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. Internal Forces: Max 0.076658634 RMS 0.063306219 Search for a local minimum. Step number 1 out of a maximum of 20 All quantities printed in internal units (Hartrees-Bohrs-Radians) Mixed Optimization -- RFO/linear search Second derivative matrix not updated -- first step. The second derivative matrix: R1 R2 A1 R1 0.87694 R2 0.00000 0.87694 A1 0.00000 0.00000 0.25000 ITU= 0 Eigenvalues --- 0.25000 0.87694 0.87694 RFO step: Lambda=-1.42103255D-02 EMin= 2.50000000D-01 Linear search not attempted -- first point. Iteration 1 RMS(Cart)= 0.08652204 RMS(Int)= 0.00160210 Iteration 2 RMS(Cart)= 0.00153550 RMS(Int)= 0.00000121 Iteration 3 RMS(Cart)= 0.00000134 RMS(Int)= 0.00000000 Iteration 4 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 2.12D-15 for atom 3. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.77714 -0.07666 0.00000 -0.08602 -0.08602 2.69112 R2 2.77714 -0.07666 0.00000 -0.08602 -0.08602 2.69112 A1 2.86688 -0.01643 0.00000 -0.06218 -0.06218 2.80469 Item Value Threshold Converged? Maximum Force 0.076659 0.000450 NO RMS Force 0.063306 0.000300 NO Maximum Displacement 0.098719 0.001800 NO RMS Displacement 0.086685 0.001200 NO Predicted change in Energy=-7.237792D-03 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.989841 0.640632 0.000000 2 8 0 -2.401226 0.830355 0.000000 3 8 0 0.404917 0.928125 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.424079 0.000000 3 O 1.424079 2.807845 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.119376 2 8 0 0.000000 -1.403923 -0.119376 3 8 0 0.000000 1.403923 -0.119376 --------------------------------------------------------------------- Rotational constants (GHZ): 554.4448922 8.0152851 7.9010641 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 53.7194063917 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Initial guess from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" B after Tr= 0.000000 0.000000 0.000000 Rot= 1.000000 0.000000 0.000000 0.000000 Ang= 0.00 deg. Initial guess orbital symmetries: Occupied (A1) (B2) (A1) (B2) (B1) (A1) (B2) (A2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. Fock symm off for IB=2 I1= 1 I= 8 J= 2 Cut=1.00D-07 Err=5.46D-04 Fock matrix is not symmetric: symmetry in diagonalization turned off. SCF Done: E(RPM6) = -0.951618625094E-01 A.U. after 12 cycles NFock= 11 Conv=0.62D-08 -V/T= 0.9875 Calling FoFJK, ICntrl= 2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 -0.000106328 0.003051769 0.000000000 2 8 0.037544906 -0.000219620 0.000000000 3 8 -0.037438578 -0.002832148 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.037544906 RMS 0.017728386 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Using GEDIIS/GDIIS optimizer. FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. Internal Forces: Max 0.037239482 RMS 0.031301355 Search for a local minimum. Step number 2 out of a maximum of 20 All quantities printed in internal units (Hartrees-Bohrs-Radians) Mixed Optimization -- RFO/linear search Update second derivatives using D2CorX and points 1 2 DE= -1.08D-02 DEPred=-7.24D-03 R= 1.50D+00 TightC=F SS= 1.41D+00 RLast= 1.37D-01 DXNew= 5.0454D-01 4.0988D-01 Trust test= 1.50D+00 RLast= 1.37D-01 DXMaxT set to 4.10D-01 The second derivative matrix: R1 R2 A1 R1 0.69076 R2 -0.18618 0.69076 A1 -0.06409 -0.06409 0.23447 ITU= 1 0 Use linear search instead of GDIIS. Eigenvalues --- 0.20688 0.53217 0.87694 RFO step: Lambda=-1.40472078D-04 EMin= 2.06879954D-01 Quartic linear search produced a step of 0.85233. Iteration 1 RMS(Cart)= 0.08376576 RMS(Int)= 0.00205085 Iteration 2 RMS(Cart)= 0.00186560 RMS(Int)= 0.00000148 Iteration 3 RMS(Cart)= 0.00000171 RMS(Int)= 0.00000000 Iteration 4 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 3.11D-15 for atom 1. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.69112 -0.03724 -0.07332 0.00107 -0.07224 2.61888 R2 2.69112 -0.03724 -0.07332 0.00107 -0.07224 2.61888 A1 2.80469 -0.01288 -0.05300 -0.02379 -0.07679 2.72790 Item Value Threshold Converged? Maximum Force 0.037239 0.000450 NO RMS Force 0.031301 0.000300 NO Maximum Displacement 0.090929 0.001800 NO RMS Displacement 0.084062 0.001200 NO Predicted change in Energy=-3.755611D-03 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.988776 0.610076 0.000000 2 8 0 -2.354173 0.847291 0.000000 3 8 0 0.356799 0.941745 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.385849 0.000000 3 O 1.385849 2.712617 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.142308 2 8 0 0.000000 -1.356308 -0.142308 3 8 0 0.000000 1.356308 -0.142308 --------------------------------------------------------------------- Rotational constants (GHZ): 390.1571751 8.5879272 8.4029657 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 54.2628065109 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Initial guess from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" B after Tr= 0.000000 0.000000 0.000000 Rot= 1.000000 0.000000 0.000000 0.000000 Ang= 0.00 deg. Initial guess orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (B2) (A2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. Fock symm off for IB=2 I1= 1 I= 8 J= 2 Cut=1.00D-07 Err=7.71D-04 Fock matrix is not symmetric: symmetry in diagonalization turned off. SCF Done: E(RPM6) = -0.984934538826E-01 A.U. after 13 cycles NFock= 12 Conv=0.26D-08 -V/T= 0.9872 Calling FoFJK, ICntrl= 2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 0.000239849 -0.006884022 0.000000000 2 8 -0.002788973 0.003349017 0.000000000 3 8 0.002549124 0.003535004 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.006884022 RMS 0.003081051 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Using GEDIIS/GDIIS optimizer. FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. Internal Forces: Max 0.007390999 RMS 0.005055880 Search for a local minimum. Step number 3 out of a maximum of 20 All quantities printed in internal units (Hartrees-Bohrs-Radians) Mixed Optimization -- RFO/linear search Update second derivatives using D2CorX and points 1 2 3 DE= -3.33D-03 DEPred=-3.76D-03 R= 8.87D-01 TightC=F SS= 1.41D+00 RLast= 1.28D-01 DXNew= 6.8933D-01 3.8342D-01 Trust test= 8.87D-01 RLast= 1.28D-01 DXMaxT set to 4.10D-01 The second derivative matrix: R1 R2 A1 R1 0.76311 R2 -0.11383 0.76311 A1 -0.08265 -0.08265 0.22693 ITU= 1 1 0 Use linear search instead of GDIIS. Eigenvalues --- 0.19674 0.67947 0.87694 RFO step: Lambda=-2.38588819D-04 EMin= 1.96739853D-01 Quartic linear search produced a step of 0.01268. Iteration 1 RMS(Cart)= 0.02006727 RMS(Int)= 0.00026549 Iteration 2 RMS(Cart)= 0.00026602 RMS(Int)= 0.00000000 Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 4.44D-16 for atom 3. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.61888 0.00332 -0.00092 0.00207 0.00116 2.62003 R2 2.61888 0.00332 -0.00092 0.00207 0.00116 2.62003 A1 2.72790 -0.00739 -0.00097 -0.03056 -0.03153 2.69638 Item Value Threshold Converged? Maximum Force 0.007391 0.000450 NO RMS Force 0.005056 0.000300 NO Maximum Displacement 0.027045 0.001800 NO RMS Displacement 0.020134 0.001200 NO Predicted change in Energy=-1.210255D-04 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.988278 0.595764 0.000000 2 8 0 -2.350366 0.854588 0.000000 3 8 0 0.352494 0.948760 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.386461 0.000000 3 O 1.386461 2.704500 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.153048 2 8 0 0.000000 -1.352250 -0.153048 3 8 0 0.000000 1.352250 -0.153048 --------------------------------------------------------------------- Rotational constants (GHZ): 337.3203510 8.6395543 8.4238013 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 54.2724920809 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Initial guess from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" B after Tr= 0.000000 0.000000 0.000000 Rot= 1.000000 0.000000 0.000000 0.000000 Ang= 0.00 deg. Initial guess orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (A2) (B2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. Fock symm off for IB=2 I1= 1 I= 8 J= 2 Cut=1.00D-07 Err=2.89D-04 Fock matrix is not symmetric: symmetry in diagonalization turned off. SCF Done: E(RPM6) = -0.987318604418E-01 A.U. after 12 cycles NFock= 11 Conv=0.43D-08 -V/T= 0.9872 Calling FoFJK, ICntrl= 2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 0.000249306 -0.007155453 0.000000000 2 8 -0.003564682 0.003457871 0.000000000 3 8 0.003315376 0.003697582 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.007155453 RMS 0.003343157 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Using GEDIIS/GDIIS optimizer. FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. Internal Forces: Max 0.007156961 RMS 0.005342475 Search for a local minimum. Step number 4 out of a maximum of 20 All quantities printed in internal units (Hartrees-Bohrs-Radians) Mixed Optimization -- RFO/linear search Update second derivatives using D2CorX and points 1 2 3 4 DE= -2.38D-04 DEPred=-1.21D-04 R= 1.97D+00 TightC=F SS= 1.41D+00 RLast= 3.16D-02 DXNew= 6.8933D-01 9.4713D-02 Trust test= 1.97D+00 RLast= 3.16D-02 DXMaxT set to 4.10D-01 The second derivative matrix: R1 R2 A1 R1 0.85058 R2 -0.02636 0.85058 A1 0.05643 0.05643 0.01156 ITU= 1 1 1 0 Use linear search instead of GDIIS. Eigenvalues --- 0.00380 0.83198 0.87694 RFO step: Lambda=-1.05966419D-04 EMin= 3.79775649D-03 Quartic linear search produced a step of 2.00000. Iteration 1 RMS(Cart)= 0.09575391 RMS(Int)= 0.00613405 Iteration 2 RMS(Cart)= 0.00644268 RMS(Int)= 0.00000380 Iteration 3 RMS(Cart)= 0.00000395 RMS(Int)= 0.00000000 Iteration 4 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 1.35D-15 for atom 3. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.62003 0.00415 0.00231 0.01284 0.01515 2.63519 R2 2.62003 0.00415 0.00231 0.01284 0.01515 2.63519 A1 2.69638 -0.00716 -0.06306 -0.08941 -0.15247 2.54391 Item Value Threshold Converged? Maximum Force 0.007157 0.000450 NO RMS Force 0.005342 0.000300 NO Maximum Displacement 0.131518 0.001800 NO RMS Displacement 0.097833 0.001200 NO Predicted change in Energy=-1.154013D-03 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.985853 0.526168 0.000000 2 8 0 -2.332015 0.890068 0.000000 3 8 0 0.331718 0.982876 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.394480 0.000000 3 O 1.394480 2.665349 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.205277 2 8 0 0.000000 -1.332674 -0.205277 3 8 0 0.000000 1.332674 -0.205277 --------------------------------------------------------------------- Rotational constants (GHZ): 187.5068052 8.8952311 8.4923578 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 54.2711961617 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Initial guess from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" B after Tr= 0.000000 0.000000 0.000000 Rot= 1.000000 0.000000 0.000000 0.000000 Ang= 0.00 deg. Initial guess orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (A2) (B2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. Fock symm off for IB=2 I1= 1 I= 8 J= 2 Cut=1.00D-07 Err=1.21D-03 Fock matrix is not symmetric: symmetry in diagonalization turned off. SCF Done: E(RPM6) = -0.997865559298E-01 A.U. after 13 cycles NFock= 12 Conv=0.44D-08 -V/T= 0.9870 Calling FoFJK, ICntrl= 2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 0.000186836 -0.005362486 0.000000000 2 8 -0.003074692 0.002577372 0.000000000 3 8 0.002887855 0.002785115 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.005362486 RMS 0.002603082 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Using GEDIIS/GDIIS optimizer. FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. Internal Forces: Max 0.004442138 RMS 0.003926090 Search for a local minimum. Step number 5 out of a maximum of 20 All quantities printed in internal units (Hartrees-Bohrs-Radians) Mixed Optimization -- RFO/linear search Update second derivatives using D2CorX and points 2 3 4 5 DE= -1.05D-03 DEPred=-1.15D-03 R= 9.14D-01 TightC=F SS= 1.41D+00 RLast= 1.54D-01 DXNew= 6.8933D-01 4.6189D-01 Trust test= 9.14D-01 RLast= 1.54D-01 DXMaxT set to 4.62D-01 The second derivative matrix: R1 R2 A1 R1 0.69673 R2 -0.18021 0.69673 A1 0.04801 0.04801 0.02735 ITU= 1 1 1 1 Use linear search instead of GDIIS. Eigenvalues --- 0.01810 0.52577 0.87694 RFO step: Lambda=-3.43490269D-05 EMin= 1.80999477D-02 Quartic linear search produced a step of 0.69834. Iteration 1 RMS(Cart)= 0.06701198 RMS(Int)= 0.00290443 Iteration 2 RMS(Cart)= 0.00312835 RMS(Int)= 0.00000108 Iteration 3 RMS(Cart)= 0.00000110 RMS(Int)= 0.00000000 Iteration 4 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 1.02D-15 for atom 3. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.63519 0.00364 0.01058 0.00557 0.01615 2.65133 R2 2.63519 0.00364 0.01058 0.00557 0.01615 2.65133 A1 2.54391 -0.00444 -0.10647 0.00208 -0.10440 2.43951 Item Value Threshold Converged? Maximum Force 0.004442 0.000450 NO RMS Force 0.003926 0.000300 NO Maximum Displacement 0.090540 0.001800 NO RMS Displacement 0.068224 0.001200 NO Predicted change in Energy=-4.594800D-04 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.984184 0.478256 0.000000 2 8 0 -2.317647 0.914554 0.000000 3 8 0 0.315681 1.006302 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.403026 0.000000 3 O 1.403026 2.634926 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.241232 2 8 0 0.000000 -1.317463 -0.241232 3 8 0 0.000000 1.317463 -0.241232 --------------------------------------------------------------------- Rotational constants (GHZ): 135.7768079 9.1018217 8.5300110 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 54.2496010803 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Initial guess from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" B after Tr= 0.000000 0.000000 0.000000 Rot= 1.000000 0.000000 0.000000 0.000000 Ang= 0.00 deg. Initial guess orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (A2) (B2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. Fock symm off for IB=2 I1= 1 I= 8 J= 2 Cut=1.00D-07 Err=9.41D-04 Fock matrix is not symmetric: symmetry in diagonalization turned off. SCF Done: E(RPM6) = -0.100133388425 A.U. after 13 cycles NFock= 12 Conv=0.38D-08 -V/T= 0.9869 Calling FoFJK, ICntrl= 2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 0.000028518 -0.000818505 0.000000000 2 8 -0.000608467 0.000388550 0.000000000 3 8 0.000579949 0.000429956 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.000818505 RMS 0.000436294 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Using GEDIIS/GDIIS optimizer. FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. Internal Forces: Max 0.000699126 RMS 0.000633901 Search for a local minimum. Step number 6 out of a maximum of 20 All quantities printed in internal units (Hartrees-Bohrs-Radians) Mixed Optimization -- En-DIIS/RFO-DIIS Update second derivatives using D2CorX and points 3 4 5 6 DE= -3.47D-04 DEPred=-4.59D-04 R= 7.55D-01 TightC=F SS= 1.41D+00 RLast= 1.07D-01 DXNew= 7.7681D-01 3.2060D-01 Trust test= 7.55D-01 RLast= 1.07D-01 DXMaxT set to 4.62D-01 The second derivative matrix: R1 R2 A1 R1 0.68206 R2 -0.19488 0.68206 A1 0.04718 0.04718 0.05257 ITU= 1 1 1 1 Use linear search instead of GDIIS. Eigenvalues --- 0.04256 0.49720 0.87694 RFO step: Lambda=-5.36155589D-07 EMin= 4.25604977D-02 Quartic linear search produced a step of 0.11169. Iteration 1 RMS(Cart)= 0.00701810 RMS(Int)= 0.00003136 Iteration 2 RMS(Cart)= 0.00003452 RMS(Int)= 0.00000000 Iteration 3 RMS(Cart)= 0.00000000 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 8.95D-16 for atom 1. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.65133 0.00070 0.00180 0.00063 0.00243 2.65376 R2 2.65133 0.00070 0.00180 0.00063 0.00243 2.65376 A1 2.43951 -0.00048 -0.01166 0.00093 -0.01073 2.42878 Item Value Threshold Converged? Maximum Force 0.000699 0.000450 NO RMS Force 0.000634 0.000300 NO Maximum Displacement 0.009456 0.001800 NO RMS Displacement 0.007032 0.001200 NO Predicted change in Energy=-5.077946D-06 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.984009 0.473252 0.000000 2 8 0 -2.316332 0.917105 0.000000 3 8 0 0.314192 1.008756 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.404311 0.000000 3 O 1.404311 2.632120 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.244987 2 8 0 0.000000 -1.316060 -0.244987 3 8 0 0.000000 1.316060 -0.244987 --------------------------------------------------------------------- Rotational constants (GHZ): 131.6461309 9.1212392 8.5302144 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 54.2429465740 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Initial guess from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" B after Tr= 0.000000 0.000000 0.000000 Rot= 1.000000 0.000000 0.000000 0.000000 Ang= 0.00 deg. Initial guess orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (A2) (B2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. Fock symm off for IB=2 I1= 1 I= 8 J= 2 Cut=1.00D-07 Err=1.08D-04 Fock matrix is not symmetric: symmetry in diagonalization turned off. SCF Done: E(RPM6) = -0.100137765815 A.U. after 11 cycles NFock= 10 Conv=0.35D-08 -V/T= 0.9869 Calling FoFJK, ICntrl= 2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 0.000000376 -0.000010800 0.000000000 2 8 0.000006767 0.000005643 0.000000000 3 8 -0.000007144 0.000005158 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.000010800 RMS 0.000005498 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Using GEDIIS/GDIIS optimizer. FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. Internal Forces: Max 0.000019883 RMS 0.000012087 Search for a local minimum. Step number 7 out of a maximum of 20 All quantities printed in internal units (Hartrees-Bohrs-Radians) Mixed Optimization -- En-DIIS/RFO-DIIS Swapping is turned off. Update second derivatives using D2CorX and points 4 5 6 7 DE= -4.38D-06 DEPred=-5.08D-06 R= 8.62D-01 TightC=F SS= 1.41D+00 RLast= 1.13D-02 DXNew= 7.7681D-01 3.3804D-02 Trust test= 8.62D-01 RLast= 1.13D-02 DXMaxT set to 4.62D-01 The second derivative matrix: R1 R2 A1 R1 0.66975 R2 -0.20719 0.66975 A1 0.03912 0.03912 0.06035 ITU= 1 1 1 1 Eigenvalues --- 0.05288 0.47003 0.87694 En-DIIS/RFO-DIIS IScMMF= 0 using points: 7 6 RFO step: Lambda= 0.00000000D+00. DidBck=F Rises=F RFO-DIIS coefs: 1.02291 -0.02291 Iteration 1 RMS(Cart)= 0.00024283 RMS(Int)= 0.00000003 Iteration 2 RMS(Cart)= 0.00000003 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 7.02D-16 for atom 3. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.65376 0.00000 0.00006 -0.00004 0.00002 2.65378 R2 2.65376 0.00000 0.00006 -0.00004 0.00002 2.65378 A1 2.42878 -0.00002 -0.00025 -0.00011 -0.00036 2.42843 Item Value Threshold Converged? Maximum Force 0.000020 0.000450 YES RMS Force 0.000012 0.000300 YES Maximum Displacement 0.000299 0.001800 YES RMS Displacement 0.000243 0.001200 YES Predicted change in Energy=-3.440727D-09 Optimization completed. -- Stationary point found. ---------------------------- ! Optimized Parameters ! ! (Angstroms and Degrees) ! -------------------------- -------------------------- ! Name Definition Value Derivative Info. ! -------------------------------------------------------------------------------- ! R1 R(1,2) 1.4043 -DE/DX = 0.0 ! ! R2 R(1,3) 1.4043 -DE/DX = 0.0 ! ! A1 A(2,1,3) 139.159 -DE/DX = 0.0 ! -------------------------------------------------------------------------------- GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.984009 0.473252 0.000000 2 8 0 -2.316332 0.917105 0.000000 3 8 0 0.314192 1.008756 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.404311 0.000000 3 O 1.404311 2.632120 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.244987 2 8 0 0.000000 -1.316060 -0.244987 3 8 0 0.000000 1.316060 -0.244987 --------------------------------------------------------------------- Rotational constants (GHZ): 131.6461309 9.1212392 8.5302144 ********************************************************************** Population analysis using the SCF density. ********************************************************************** Orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (A2) (B2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) The electronic state is 1-A1. Alpha occ. eigenvalues -- -1.19676 -1.12967 -0.74430 -0.56854 -0.55395 Alpha occ. eigenvalues -- -0.54777 -0.44871 -0.44785 -0.36033 Alpha virt. eigenvalues -- -0.02177 0.00737 0.10701 0.30013 0.30768 Alpha virt. eigenvalues -- 0.31071 0.32318 0.34857 Condensed to atoms (all electrons): 1 2 3 1 S 4.870545 0.000000 0.000000 2 O 0.000000 6.564727 0.000000 3 O 0.000000 0.000000 6.564727 Mulliken charges: 1 1 S 1.129455 2 O -0.564727 3 O -0.564727 Sum of Mulliken charges = 0.00000 Mulliken charges with hydrogens summed into heavy atoms: 1 1 S 1.129455 2 O -0.564727 3 O -0.564727 Charge= 0.0000 electrons Dipole moment (field-independent basis, Debye): X= 0.0000 Y= 0.0000 Z= 1.9398 Tot= 1.9398 N-N= 5.424294657397D+01 E-N=-8.904503003594D+01 KE=-7.645369566297D+00 Symmetry A1 KE=-3.813676452523D+00 Symmetry A2 KE=-4.432018806378D-01 Symmetry B1 KE=-6.627235754675D-01 Symmetry B2 KE=-2.725767657669D+00 1|1| IMPERIAL COLLEGE-CHWS-263|FOpt|RPM6|ZDO|O2S1|QL2415|20-Nov-2017|0 ||# opt freq pm6 geom=connectivity integral=grid=ultrafine||Title Card Required||0,1|S,-0.9840092019,0.473252299,0.|O,-2.3163322523,0.917104 591,0.|O,0.3141917522,1.0087556605,0.||Version=EM64W-G09RevD.01|State= 1-A1|HF=-0.1001378|RMSD=3.477e-009|RMSF=5.498e-006|Dipole=0.0265733,-0 .762695,0.|PG=C02V [C2(S1),SGV(O2)]||@ HAPPINESS IS NOT HAVING WHAT YOU WANT -- HAPPINESS IS WANTING WHAT YOU HAVE! -- FROM MRS. SEVERN'S DESK Job cpu time: 0 days 0 hours 0 minutes 16.0 seconds. File lengths (MBytes): RWF= 5 Int= 0 D2E= 0 Chk= 2 Scr= 1 Normal termination of Gaussian 09 at Mon Nov 20 22:37:31 2017. Link1: Proceeding to internal job step number 2. ------------------------------------------------------------- #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RPM6/ZDO Freq ------------------------------------------------------------- 1/10=4,29=7,30=1,38=1,40=1/1,3; 2/12=2,40=1/2; 3/5=2,14=-4,16=1,25=1,41=3900000,70=2,71=2,75=-5,116=1,135=40,140=1/1,2,3; 4/5=101,35=1/1; 5/5=2,35=1,98=1/2; 8/6=4,10=90,11=11/1; 11/6=1,8=1,9=11,15=111,16=1/1,2,10; 10/6=1/2; 6/7=2,8=2,9=2,10=2,18=1,28=1/1; 7/8=1,10=1,25=1/1,2,3,16; 1/10=4,30=1/3; 99//99; Structure from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" ------------------- Title Card Required ------------------- Charge = 0 Multiplicity = 1 Redundant internal coordinates found in file. S,0,-0.9840092019,0.473252299,0. O,0,-2.3163322523,0.917104591,0. O,0,0.3141917522,1.0087556605,0. Recover connectivity data from disk. GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Initialization pass. ---------------------------- ! Initial Parameters ! ! (Angstroms and Degrees) ! -------------------------- -------------------------- ! Name Definition Value Derivative Info. ! -------------------------------------------------------------------------------- ! R1 R(1,2) 1.4043 calculate D2E/DX2 analytically ! ! R2 R(1,3) 1.4043 calculate D2E/DX2 analytically ! ! A1 A(2,1,3) 139.159 calculate D2E/DX2 analytically ! -------------------------------------------------------------------------------- Trust Radius=3.00D-01 FncErr=1.00D-07 GrdErr=1.00D-07 Number of steps in this run= 2 maximum allowed number of steps= 2. GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Input orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 -0.984009 0.473252 0.000000 2 8 0 -2.316332 0.917105 0.000000 3 8 0 0.314192 1.008756 0.000000 --------------------------------------------------------------------- Distance matrix (angstroms): 1 2 3 1 S 0.000000 2 O 1.404311 0.000000 3 O 1.404311 2.632120 0.000000 Stoichiometry O2S Framework group C2V[C2(S),SGV(O2)] Deg. of freedom 2 Full point group C2V NOp 4 Largest Abelian subgroup C2V NOp 4 Largest concise Abelian subgroup C2 NOp 2 Standard orientation: --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------- 1 16 0 0.000000 0.000000 0.244987 2 8 0 0.000000 -1.316060 -0.244987 3 8 0 0.000000 1.316060 -0.244987 --------------------------------------------------------------------- Rotational constants (GHZ): 131.6461309 9.1212392 8.5302144 Standard basis: VSTO-6G (5D, 7F) There are 8 symmetry adapted cartesian basis functions of A1 symmetry. There are 2 symmetry adapted cartesian basis functions of A2 symmetry. There are 3 symmetry adapted cartesian basis functions of B1 symmetry. There are 5 symmetry adapted cartesian basis functions of B2 symmetry. There are 7 symmetry adapted basis functions of A1 symmetry. There are 2 symmetry adapted basis functions of A2 symmetry. There are 3 symmetry adapted basis functions of B1 symmetry. There are 5 symmetry adapted basis functions of B2 symmetry. 17 basis functions, 108 primitive gaussians, 18 cartesian basis functions 9 alpha electrons 9 beta electrons nuclear repulsion energy 54.2429465740 Hartrees. Integral buffers will be 131072 words long. Regular integral format. Two-electron integral symmetry is turned off. Do NDO integrals. One-electron integrals computed using PRISM. NBasis= 17 RedAO= T EigKep= 1.00D+00 NBF= 7 2 3 5 NBsUse= 17 1.00D-06 EigRej= -1.00D+00 NBFU= 7 2 3 5 Initial guess from the checkpoint file: "\\icnas3.cc.ic.ac.uk\ql2415\Desktop\computational\Ex3\SO2_MIN_PM6.chk" B after Tr= 0.000000 0.000000 0.000000 Rot= 1.000000 0.000000 0.000000 0.000000 Ang= 0.00 deg. Initial guess orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (A2) (B2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) Overlap will be assumed to be unity. Keep J ints in memory in canonical form, NReq=1872442. Requested convergence on RMS density matrix=1.00D-08 within 128 cycles. Requested convergence on MAX density matrix=1.00D-06. Requested convergence on energy=1.00D-06. No special actions if energy rises. SCF Done: E(RPM6) = -0.100137765815 A.U. after 2 cycles NFock= 1 Conv=0.63D-09 -V/T= 0.9869 Range of M.O.s used for correlation: 1 17 NBasis= 17 NAE= 9 NBE= 9 NFC= 0 NFV= 0 NROrb= 17 NOA= 9 NOB= 9 NVA= 8 NVB= 8 Symmetrizing basis deriv contribution to polar: IMax=3 JMax=2 DiffMx= 0.00D+00 G2DrvN: will do 4 centers at a time, making 1 passes. Calling FoFCou, ICntrl= 3107 FMM=F I1Cent= 0 AccDes= 0.00D+00. End of G2Drv F.D. properties file 721 does not exist. End of G2Drv F.D. properties file 722 does not exist. End of G2Drv F.D. properties file 788 does not exist. IDoAtm=111 Differentiating once with respect to electric field. with respect to dipole field. Differentiating once with respect to nuclear coordinates. Electric field/nuclear overlap derivatives assumed to be zero. Keep J ints in memory in canonical form, NReq=1855126. There are 9 degrees of freedom in the 1st order CPHF. IDoFFX=4 NUNeed= 9. LinEq1: Iter= 0 NonCon= 9 RMS=6.61D-01 Max=3.27D+00 NDo= 9 AX will form 9 AO Fock derivatives at one time. LinEq1: Iter= 1 NonCon= 9 RMS=1.54D-01 Max=1.05D+00 NDo= 9 LinEq1: Iter= 2 NonCon= 9 RMS=2.34D-02 Max=1.18D-01 NDo= 9 LinEq1: Iter= 3 NonCon= 9 RMS=4.32D-03 Max=1.82D-02 NDo= 9 LinEq1: Iter= 4 NonCon= 9 RMS=6.11D-04 Max=3.11D-03 NDo= 9 LinEq1: Iter= 5 NonCon= 9 RMS=6.48D-05 Max=2.94D-04 NDo= 9 LinEq1: Iter= 6 NonCon= 9 RMS=6.25D-06 Max=2.28D-05 NDo= 9 LinEq1: Iter= 7 NonCon= 9 RMS=1.40D-06 Max=4.89D-06 NDo= 9 LinEq1: Iter= 8 NonCon= 5 RMS=2.73D-07 Max=1.10D-06 NDo= 9 LinEq1: Iter= 9 NonCon= 2 RMS=4.03D-08 Max=1.53D-07 NDo= 9 LinEq1: Iter= 10 NonCon= 0 RMS=5.13D-09 Max=1.42D-08 NDo= 9 Linear equations converged to 1.000D-08 1.000D-07 after 10 iterations. Isotropic polarizability for W= 0.000000 24.44 Bohr**3. End of Minotr F.D. properties file 721 does not exist. End of Minotr F.D. properties file 722 does not exist. End of Minotr F.D. properties file 788 does not exist. ********************************************************************** Population analysis using the SCF density. ********************************************************************** Orbital symmetries: Occupied (A1) (B2) (A1) (B1) (A1) (B2) (A2) (B2) (A1) Virtual (B1) (A1) (B2) (A1) (B1) (A1) (A2) (B2) The electronic state is 1-A1. Alpha occ. eigenvalues -- -1.19676 -1.12967 -0.74430 -0.56854 -0.55395 Alpha occ. eigenvalues -- -0.54777 -0.44871 -0.44785 -0.36033 Alpha virt. eigenvalues -- -0.02177 0.00737 0.10701 0.30013 0.30768 Alpha virt. eigenvalues -- 0.31071 0.32318 0.34857 Condensed to atoms (all electrons): 1 2 3 1 S 4.870545 0.000000 0.000000 2 O 0.000000 6.564727 0.000000 3 O 0.000000 0.000000 6.564727 Mulliken charges: 1 1 S 1.129455 2 O -0.564727 3 O -0.564727 Sum of Mulliken charges = 0.00000 Mulliken charges with hydrogens summed into heavy atoms: 1 1 S 1.129455 2 O -0.564727 3 O -0.564727 APT charges: 1 1 S 1.168104 2 O -0.584051 3 O -0.584051 Sum of APT charges = 0.00000 APT charges with hydrogens summed into heavy atoms: 1 1 S 1.168104 2 O -0.584051 3 O -0.584051 Charge= 0.0000 electrons Dipole moment (field-independent basis, Debye): X= 0.0000 Y= 0.0000 Z= 1.9398 Tot= 1.9398 N-N= 5.424294657397D+01 E-N=-8.904503003423D+01 KE=-7.645369564892D+00 Symmetry A1 KE=-3.813676452599D+00 Symmetry A2 KE=-4.432018801055D-01 Symmetry B1 KE=-6.627235753358D-01 Symmetry B2 KE=-2.725767656851D+00 Exact polarizability: 11.288 0.000 52.574 0.000 0.000 9.461 Approx polarizability: 8.350 0.000 60.497 0.000 0.000 8.521 Calling FoFJK, ICntrl= 100127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0. Full mass-weighted force constant matrix: Low frequencies --- -4.3921 -0.0175 -0.0013 0.0074 1.7195 2.1503 Low frequencies --- 224.3042 992.6798 1284.3380 Diagonal vibrational polarizability: 0.0000000 3.3450847 39.2661789 Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering activities (A**4/AMU), depolarization ratios for plane and unpolarized incident light, reduced masses (AMU), force constants (mDyne/A), and normal coordinates: 1 2 3 A1 A1 B2 Frequencies -- 224.3042 992.6798 1284.3380 Red. masses -- 20.3595 16.5846 20.8739 Frc consts -- 0.6035 9.6288 20.2867 IR Inten -- 72.9793 8.4522 205.0372 Atom AN X Y Z X Y Z X Y Z 1 16 0.00 0.00 0.52 0.00 0.00 -0.19 0.00 0.55 0.00 2 8 0.00 0.30 -0.52 0.00 0.67 0.19 0.00 -0.55 -0.21 3 8 0.00 -0.30 -0.52 0.00 -0.67 0.19 0.00 -0.55 0.21 ------------------- - Thermochemistry - ------------------- Temperature 298.150 Kelvin. Pressure 1.00000 Atm. Atom 1 has atomic number 16 and mass 31.97207 Atom 2 has atomic number 8 and mass 15.99491 Atom 3 has atomic number 8 and mass 15.99491 Molecular mass: 63.96190 amu. Principal axes and moments of inertia in atomic units: 1 2 3 Eigenvalues -- 13.70903 197.86140 211.57044 X 0.00000 0.00000 1.00000 Y 1.00000 0.00000 0.00000 Z 0.00000 1.00000 0.00000 This molecule is an asymmetric top. Rotational symmetry number 2. Rotational temperatures (Kelvin) 6.31801 0.43775 0.40939 Rotational constants (GHZ): 131.64613 9.12124 8.53021 Zero-point vibrational energy 14961.2 (Joules/Mol) 3.57582 (Kcal/Mol) Warning -- explicit consideration of 1 degrees of freedom as vibrations may cause significant error Vibrational temperatures: 322.72 1428.24 1847.87 (Kelvin) Zero-point correction= 0.005698 (Hartree/Particle) Thermal correction to Energy= 0.009104 Thermal correction to Enthalpy= 0.010049 Thermal correction to Gibbs Free Energy= -0.018477 Sum of electronic and zero-point Energies= -0.094439 Sum of electronic and thermal Energies= -0.091033 Sum of electronic and thermal Enthalpies= -0.090089 Sum of electronic and thermal Free Energies= -0.118614 E (Thermal) CV S KCal/Mol Cal/Mol-Kelvin Cal/Mol-Kelvin Total 5.713 8.307 60.036 Electronic 0.000 0.000 0.000 Translational 0.889 2.981 38.386 Rotational 0.889 2.981 19.601 Vibrational 3.936 2.345 2.050 Vibration 1 0.649 1.804 1.924 Q Log10(Q) Ln(Q) Total Bot 0.315234D+09 8.498633 19.568826 Total V=0 0.131742D+12 11.119724 25.604110 Vib (Bot) 0.365652D-02 -2.436932 -5.611243 Vib (Bot) 1 0.880251D+00 -0.055394 -0.127549 Vib (V=0) 0.152812D+01 0.184159 0.424041 Vib (V=0) 1 0.151234D+01 0.179651 0.413661 Electronic 0.100000D+01 0.000000 0.000000 Translational 0.201065D+08 7.303337 16.816555 Rotational 0.428773D+04 3.632228 8.363514 ***** Axes restored to original set ***** ------------------------------------------------------------------- Center Atomic Forces (Hartrees/Bohr) Number Number X Y Z ------------------------------------------------------------------- 1 16 0.000000376 -0.000010803 0.000000000 2 8 0.000006766 0.000005644 0.000000000 3 8 -0.000007142 0.000005159 0.000000000 ------------------------------------------------------------------- Cartesian Forces: Max 0.000010803 RMS 0.000005498 FormGI is forming the generalized inverse of G from B-inverse, IUseBI=4. GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Internal Forces: Max 0.000019884 RMS 0.000012088 Search for a local minimum. Step number 1 out of a maximum of 2 All quantities printed in internal units (Hartrees-Bohrs-Radians) Second derivative matrix not updated -- analytic derivatives used. The second derivative matrix: R1 R2 A1 R1 0.54138 R2 0.00993 0.54138 A1 0.05946 0.05946 0.07081 ITU= 0 Eigenvalues --- 0.05652 0.53145 0.56561 Angle between quadratic step and forces= 24.86 degrees. Linear search not attempted -- first point. Iteration 1 RMS(Cart)= 0.00022063 RMS(Int)= 0.00000003 Iteration 2 RMS(Cart)= 0.00000003 RMS(Int)= 0.00000000 ClnCor: largest displacement from symmetrization is 1.46D-15 for atom 3. Variable Old X -DE/DX Delta X Delta X Delta X New X (Linear) (Quad) (Total) R1 2.65376 0.00000 0.00000 0.00003 0.00003 2.65379 R2 2.65376 0.00000 0.00000 0.00003 0.00003 2.65379 A1 2.42878 -0.00002 0.00000 -0.00033 -0.00033 2.42846 Item Value Threshold Converged? Maximum Force 0.000020 0.000450 YES RMS Force 0.000012 0.000300 YES Maximum Displacement 0.000276 0.001800 YES RMS Displacement 0.000221 0.001200 YES Predicted change in Energy=-3.113844D-09 Optimization completed. -- Stationary point found. ---------------------------- ! Optimized Parameters ! ! (Angstroms and Degrees) ! -------------------------- -------------------------- ! Name Definition Value Derivative Info. ! -------------------------------------------------------------------------------- ! R1 R(1,2) 1.4043 -DE/DX = 0.0 ! ! R2 R(1,3) 1.4043 -DE/DX = 0.0 ! ! A1 A(2,1,3) 139.159 -DE/DX = 0.0 ! -------------------------------------------------------------------------------- GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad 1|1| IMPERIAL COLLEGE-CHWS-263|Freq|RPM6|ZDO|O2S1|QL2415|20-Nov-2017|0 ||#N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RPM6/ZDO Freq||Title Card Required||0,1|S,-0.9840092019,0.473252299,0.|O,-2.3163322523,0.9 17104591,0.|O,0.3141917522,1.0087556605,0.||Version=EM64W-G09RevD.01|S tate=1-A1|HF=-0.1001378|RMSD=6.282e-010|RMSF=5.498e-006|ZeroPoint=0.00 56984|Thermal=0.0091044|Dipole=0.0265733,-0.762695,0.|DipoleDeriv=1.76 60422,0.021334,0.,0.021334,1.1544685,0.,0.,0.,0.5838025,-0.8934655,-0. 0589978,0.,0.3370707,-0.5667893,0.,0.,0.,-0.2918996,-0.8725766,0.03766 38,0.,-0.3584047,-0.5876781,0.,0.,0.,-0.2918996|Polar=52.5213237,1.500 2928,9.5129297,0.,0.,11.2883911|HyperPolar=9.011693,-86.001469,-6.2454 791,6.6069555,0.,0.,0.,-0.169561,4.8666562,0.|PG=C02V [C2(S1),SGV(O2)] |NImag=0||0.93250821,0.02862435,0.11194341,0.,0.,-0.00001171,-0.477165 89,0.12509828,0.,0.50174097,0.15908383,-0.04506000,0.,-0.14139547,0.04 969787,0.,0.,0.00000584,0.,0.,-0.00000151,-0.45534218,-0.15372261,0.,- 0.02457516,-0.01768831,0.,0.47991728,-0.18770816,-0.06688371,0.,0.0162 9732,-0.00463771,0.,0.17141078,0.07152156,0.,0.,0.00000584,0.,0.,-0.00 000431,0.,0.,-0.00000151||-0.00000038,0.00001080,0.,-0.00000677,-0.000 00564,0.,0.00000714,-0.00000516,0.|||@ HAPPINESS IS NOT HAVING WHAT YOU WANT -- HAPPINESS IS WANTING WHAT YOU HAVE! -- FROM MRS. SEVERN'S DESK Job cpu time: 0 days 0 hours 0 minutes 3.0 seconds. File lengths (MBytes): RWF= 5 Int= 0 D2E= 0 Chk= 2 Scr= 1 Normal termination of Gaussian 09 at Mon Nov 20 22:37:34 2017.